US20160138139A1 - Spheroidizing treatment method for molten metal of spheroidal graphite cast iron - Google Patents

Spheroidizing treatment method for molten metal of spheroidal graphite cast iron Download PDF

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Publication number
US20160138139A1
US20160138139A1 US14/897,084 US201414897084A US2016138139A1 US 20160138139 A1 US20160138139 A1 US 20160138139A1 US 201414897084 A US201414897084 A US 201414897084A US 2016138139 A1 US2016138139 A1 US 2016138139A1
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Prior art keywords
graphite
molten metal
spheroidizing
added
treatment method
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US14/897,084
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English (en)
Inventor
Ryosuke Fujimoto
Shuhei Homma
Takashi Yokoyama
Yuji Nihei
Toshiaki Ozeki
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Shibaura Machine Co Ltd
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Toshiba Machine Co Ltd
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Assigned to TOSHIBA KIKAI KABUSHIKI KAISHA reassignment TOSHIBA KIKAI KABUSHIKI KAISHA ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FUJIMOTO, RYOSUKE, HONMA, SHUHEI, NIHEI, YUJI, OZEKI, TOSHIAKI, YOKOYAMA, TAKASHI
Publication of US20160138139A1 publication Critical patent/US20160138139A1/en
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D1/00—Treatment of fused masses in the ladle or the supply runners before casting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
    • B22D27/20—Measures not previously mentioned for influencing the grain structure or texture; Selection of compositions therefor
    • 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
    • C21C1/10—Making spheroidal graphite cast-iron
    • C21C1/105—Nodularising additive agents
    • 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
    • C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
    • 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
    • C22C33/10—Making cast-iron alloys including procedures for adding magnesium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C37/00—Cast-iron alloys
    • C22C37/04—Cast-iron alloys containing spheroidal graphite
    • C—CHEMISTRY; METALLURGY
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium

Definitions

  • the present invention relates to a spheroidizing treatment method for a molten metal of a spheroidal graphite cast iron.
  • Spheroidal graphite cast iron is a material, in which graphite is spheroidized in its as-cast state, and which has excellent mechanical properties (Young's modulus, tensile strength, and elongation).
  • the spheroidization of graphite is conducted by adding a graphite spheroidizing agent in a ladle.
  • the graphite spheroidizing agent contains Mg, rare earth (hereinafter abbreviated to “RE”), Ca, Al and so on.
  • chunky graphite which is an abnormal graphite structure is likely to be crystallized in the metallographic structure of the spheroidal graphite cast iron.
  • the crystallization of the chunky graphite results in significant reduction of Young's modulus, tensile strength and elongation of the cast iron material.
  • JP2007182620A An example of a graphite spheroidizing agent for suppressing generation of chunky graphite is disclosed in JP2007182620A.
  • JP2007182620A fails to teach a preferable amount of the graphite spheroidizing agent to be added to the molten metal.
  • a graphite spheroidizing agent to be used contains: 30-80 wt % of Si; Mg; RE (rare earth element) which comprises Ce with a purity level of 80-100 wt % or La with a purity level of 80-100 wt %; Ca; and Al.
  • RE rare earth element
  • the balance of the graphite spheroidizing agent contains iron and unavoidable impurities.
  • the graphite spheroidizing agent may further contain S as an optional element.
  • the graphite spheroidizing agent is added to the molten metal such that an amount of RE equivalent to 0.001-0.009 wt % of the total weight of the molten metal, an amount of Ca equivalent to 0.001-0.02 wt % of the total weight of the molten metal, and an amount of Al equivalent to 0.001-0.02 wt % of the total weight of the molten metal are added to the molten metal, and such that the molten metal contains 0.03-0.07 wt % of Mg after the graphite spheroidizing treatment.
  • the contents of RE, Ca, and Al which show a graphitizing effect and accelerate crystallization of chunky graphite are lowered but optimized. Therefore, it is possible to suppress crystallization of chunky graphite in a thick section of spheroidal graphite cast iron, particularly in a thick section where the eutectic solidification time is 1.0 ks (i.e., 1000 seconds) or more.
  • the amounts of Ca and Al which promote formation of slag and dross are reduced but optimized. Therefore, a clean molten metal can be obtained. As a result, a product having less defects such as slag inclusion and pinholes can be obtained.
  • FIG. 1 is an optical microphotograph showing an example of the structure of a sound spheroidal graphite cast iron.
  • FIG. 2 is an optical microphotograph showing an example of a structure in which chunky graphite has been crystallized.
  • FIG. 3 is a schematic illustration of a graphite spheroidizing treatment by a sandwich method.
  • FIG. 4 is a schematic illustration of a graphite spheroidizing treatment by a wire feeder method.
  • the shape of products to which the graphite spheroidizing treatment method in this embodiment is applied is not limited.
  • the graphite spheroidizing treatment method achieves an excellent structure-improving effect especially on those products having a eutectic solidification time of 1.0 ks or more, for example, in a range of 1.0-100 ks, or those products having a maximum wall thickness of 100-500 mm.
  • the graphite spheroidizing agent used in the embodiment of the graphite spheroidizing treatment method of the present invention contains 30-80 wt % of Si (silicon); Mg (magnesium); RE (rare earth element); Ca (calcium); and Al (aluminum).
  • the graphite spheroidizing agent is added to the molten metal so as to satisfy the following two conditions.
  • the first condition is that the adding amounts of the following elements to the molten metal (the ratio of the weight of the added elements to the total weight of the molten metal) are RE: 0.001-0.009 wt %; Ca: 0.001-0.02 wt %; Al: 0.001-0.02 wt %.
  • the second condition is that the molten metal contains 0.03-0.07 wt % Mg after the graphite spheroidizing treatment.
  • the graphite spheroidizing agent may further contain S.
  • the parts of the graphite spheroidizing agent other than the aforementioned elements typically consist of Fe (iron) and unavoidable impurities.
  • Mg added to the molten metal takes part in nucleation of graphite, part of the Mg does not serve as a nucleus for graphite but becomes an oxide or a composite compound with the RE and so on, with the oxide or composite compound being wasted as slag. Therefore, it is preferable for Mg to be added to the molten metal in such an addition amount that after the graphite spheroidizing treatment (namely, immediately before casting into a mold) the Mg will remain in the molten metal in an amount for maintaining a graphite spheroidizing effect, specifically, in an amount of 0.03-0.07 wt %.
  • the content of Mg in the molten metal after the graphite spheroidizing treatment is less than 0.03 wt %, graphite shape deteriorates due to deficiency in the deoxidizing effect of Mg and deficiency in the amount of Mg serving as a raw material for graphite nuclei. If the Mg content exceeds 0.07 wt %, on the other hand, exploded graphite is formed. In either case, the graphite shape is deteriorated, and mechanical properties are degraded accordingly.
  • the aforementioned value for the amount of Mg is an ordinary value in the manufacture of spheroidal graphite cast iron.
  • the relationship between the amount of Mg added to the molten metal and the Mg content of the molten metal after the graphite spheroidizing treatment is well known to those skilled in the art.
  • a spheroidizing agent containing 5 wt % of Mg is added to the molten metal in an amount of 1.5 wt % (namely, where Mg is added to the molten metal in an amount of 0.075%)
  • the Mg content (analyzed value) of the molten metal after the graphite spheroidizing treatment will be 0.035-0.055 wt %. It is also well known that an increase in the amount of Mg added lowers the yield of Mg.
  • RE is used as a constituent of the graphite spherodizing agent
  • it is a common practice to use the RE in the form of an alloy (misch metal) in which Ce:La 2:1.
  • the misch metal is further subjected to refining or purification, and high-purity Ce or La is added solely.
  • the ratio of the amount of RE added to the molten metal to the amount of S (sulfur) added to the molten metal is preferably set in the range of 0.06-1.60 (in a case where 0.005-0.030 wt % of S and 0.002-0.008 wt % of RE are added to the molten metal). According to this setting, it is possible to more reliably obtain a good graphite shape. It should be noted that it has been said that an RE/S ratio in the range of 2.0-5.0 is recommendable for obtaining a good graphite shape in a case of thin-walled products.
  • the molten metal of a cast iron may contain a comparatively large amount of S (it may depend on the used melting furnace or the used melting method).
  • the S is positively added as mentioned above if the molten metal (raw molten metal) has been sufficiently desulfurized. Where S is contained in a comparatively large amount in the raw molten metal, the positive S addition may be avoided; or, alternatively, S may be added in an amount obtained by subtracting the amount of S originally contained in the raw molten metal from the necessary amount.
  • the product obtained may have such defects as slag inclusion and pinholes.
  • FIG. 1 an example of a good graphite shape appearing in a casting with a eutectic solidification time of 2.5 ks is shown in the photograph in FIG. 1
  • FIG. 2 an example of a bad graphite shape is shown in the photograph in FIG. 2 .
  • a lot of crystallization of chunky graphite is seen, particularly at the left, in the photograph in FIG. 2 .
  • the amounts of RE, Ca, and Al added were optimized as aforementioned, whereas in the example of FIG. 2 , Ca and Al were added in excessive amounts.
  • the graphite spheroidizing agent as above is applicable to all the known graphite spheroidizing treatment methods exemplified by, but not limited to, a sandwich method, a tundish method, and a wire feeder method.
  • FIG. 3 schematically illustrates the sandwich method.
  • a reaction groove (pocket) formed in a bottom portion of a ladle is filled with a graphite spheroidizing agent SA, which is thoroughly covered with a covering agent CA (scrap iron, Fe—Si, etc.).
  • Raw molten metal RM at 1400-1500° C. is poured into the ladle, and the spheroidizing treatment of graphite is effected through the reaction between the graphite spheroidizing agent and the molten metal.
  • a larger amount of Mg addition results in a more vigorous reaction.
  • Such a vigorous reaction may be moderated by adding Ca in a larger amount within the optimum range.
  • RE 0.1-0.6 wt % (where RE is comprised of Ce with a purity level of 80-100 wt %, or La with a purity level of 80-100 wt %), preferably, 0.2-0.5 wt %
  • the graphite spheroidizing agent for use in the sandwich method for example, the followings are adopted.
  • a particulate graphite spheroidizing agent with a particle diameter of 1-5 mm is preferably used so as to ensure complete melting of the agent.
  • a lumpy graphite spheroidizing agent with a particle diameter of 5-70 mm is preferably used so as to suppress fading as much as possible.
  • FIG. 4 schematically illustrates the wire feeder method.
  • a raw molten material at 1400-1500° C. is poured into the ladle, and then the lid is closed.
  • a predetermined length portion of a wire W is fed into the molten metal MM by a feeder (not shown) (see the arrow in the figure).
  • a feeder not shown
  • the wire there can be used, for example, a wire-shaped member wherein a graphite spheroidizing agent with a particle diameter of 0.1 to 1 mm is sealed in an inner cavity of a hollow sheath member made of iron.
  • RE 0.3-1.8 wt % (where RE is comprised of Ce with a purity level of 80-100 wt %, or La with a purity level of 80-100 wt %)
  • the graphite spheroidizing agent may further contain S.
  • the molten metal having undergone the graphite spheroidizing treatment is cast into a mold at a temperature of 1300-1400° C., whereby a thick-walled spheroidal graphite cast iron product having good mechanical properties is obtained.
  • a thick-walled product having a eutectic solidification time longer than 1 ks it is preferable to set the casting temperature to a lower value, for example, 1270-1370° C.
  • mechanical properties can further be improved by conducting inoculation after the graphite spheroidizing treatment.
  • an inoculant having a composition of Fe-(30-75 wt %)Si-(0-3.0 wt %)Ca-(0-3.0 wt %)Al-(0-1.0 wt %)Ba may be used.
  • An addition of the inoculant in an amount per run of 0.01-0.20 wt % (the weight of the inoculant/the weight of the molten metal) may be conducted one to five times.
  • Such an inoculation is not limited to the one conducted in the ladle, before it is poured into the mold, but may be conducted during or concurrently with the pouring into the mold, as in the cases of pouring of basin inoculation and in-mold inoculation.
  • a particulate graphite spheroidizing agent having the following composition was prepared.
  • the aforementioned graphite spheroidizing agent was added to 30 kg of a raw molten metal.
  • the graphite spheroidizing agent was added to the raw molten material in an amount of about 1.5 wt % so that the amounts of the constituent elements added to the molten metal, based on the weight of the molten metal, would be as follows.
  • the amount of Mg contained in the molten metal after the graphite spheroidizing treatment was about 0.045 wt %.
  • Samples Nos. 26-29 were subjected, after the graphite spheroidizing treatment and before the casting into a mold, to inoculation using the aforementioned inoculant in a ladle twice, and immediately (so immediately that fading would not occur) thereafter, casting was conducted.
  • the composition values for Sample Nos. 26-29 are the values after the graphite spheroidizing treatment and before the inoculation.
  • test pieces After the test pieces were cast, they were processed into a predetermined shape, and subjected to a tensile test to measure tensile strength and elongation. In addition, the hardness of the test pieces was measured, and, further, microstructure observation under microscope and measurement of spheroidal graphite rate (percent nodularity) were carried out. These tests were all carried out in accordance with the requirements specified for spheroidal graphite cast iron (JIS G 5502) in the Japanese Industrial Standards.
  • Condition 1 RE is Ce alone or La alone.
  • Condition 2 The amount of RE added is in the range of 0.001-0.009 wt %.
  • Condition 3 The amount of Ca added is in the range of 0.001-0.02 wt %.
  • Condition 4 The amount of Al added is in the range of 0.001-0.02 wt %.
  • the tensile strength was partially below 450 MPa in the condition where the amount of RE after the graphite spheroidizing treatment was 0.019 wt %, the tensile strength was not less than 450 MPa in the other conditions. Even where the amount of RE was small, elongation tended to be lowered when the Ca and Al addition amounts were 0.03% and when the Ce—La alloy was used as RE.
  • the reference values for mechanical properties applied to cast iron products with a chief thickness of 60-200 mm in FCD 400-15A and FCD 500-7A described in Table 3 “Mechanical properties of cast-on test sample” of JIS G 5502 were taken into consideration.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
US14/897,084 2013-09-06 2014-09-05 Spheroidizing treatment method for molten metal of spheroidal graphite cast iron Abandoned US20160138139A1 (en)

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JP2013-184928 2013-09-06
JP2013184928 2013-09-06
PCT/JP2014/073534 WO2015034062A1 (ja) 2013-09-06 2014-09-05 球状黒鉛鋳鉄の溶湯の球状化処理方法

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JP (1) JP6258336B2 (zh)
KR (1) KR101708583B1 (zh)
CN (1) CN104903470B (zh)
DE (1) DE112014004110T5 (zh)
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US11433927B1 (en) * 2012-11-15 2022-09-06 Pennsy Corporation Lightweight fatigue resistant railcar truck, sideframe and bolster
CN117363835A (zh) * 2023-10-01 2024-01-09 山东友达新材料科技有限公司 一种高纯球化包芯线及其制备方法

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JP6728150B2 (ja) 2015-05-18 2020-07-22 芝浦機械株式会社 鋳鉄溶湯処理方法
JP7237343B2 (ja) * 2018-12-25 2023-03-13 東洋電化工業株式会社 鋳鉄用黒鉛球状化剤
MX2019007412A (es) * 2019-06-20 2019-08-29 Francisco Alfonso Labrador Rodriguez Aditivo para tratar hierro en fundicion para producir hierro fundido de contraccion cero y con grafito esferoidal tipo lonsdaleita.
CN111621689A (zh) * 2020-04-16 2020-09-04 江苏力源金河铸造有限公司 一种消除球墨铸铁反白口现象的熔炼工艺方法
DE112021005605T5 (de) 2020-10-23 2023-08-03 Hinode, Ltd. Eisenlegierungsmaterial zum giessen und eisenguss
WO2022202914A1 (ja) * 2021-03-24 2022-09-29 日立金属株式会社 球状黒鉛鋳鉄、球状黒鉛鋳鉄の製造方法及び球状化処理剤

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KR20160002674A (ko) 2016-01-08
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