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WO2024209040A1 - Additif de traitement de métaux - Google Patents

Additif de traitement de métaux Download PDF

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Publication number
WO2024209040A1
WO2024209040A1 PCT/EP2024/059311 EP2024059311W WO2024209040A1 WO 2024209040 A1 WO2024209040 A1 WO 2024209040A1 EP 2024059311 W EP2024059311 W EP 2024059311W WO 2024209040 A1 WO2024209040 A1 WO 2024209040A1
Authority
WO
WIPO (PCT)
Prior art keywords
inoculant composition
active agent
inoculant
composition according
molten iron
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.)
Pending
Application number
PCT/EP2024/059311
Other languages
English (en)
Inventor
Colin Powell
Wolfram Stets
Wolfgang Troschel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Foseco International Ltd
Original Assignee
Foseco International Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Foseco International Ltd filed Critical Foseco International Ltd
Priority to CN202480023663.7A priority Critical patent/CN120936733A/zh
Priority to AU2024243614A priority patent/AU2024243614A1/en
Publication of WO2024209040A1 publication Critical patent/WO2024209040A1/fr
Priority to MX2025011881A priority patent/MX2025011881A/es
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/04—Making ferrous alloys by melting
    • 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
    • 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
    • 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
    • C21C7/0037—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 by injecting powdered material
    • 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
    • C21C7/0056—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 using cored wires
    • 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 methods for treating molten metal.
  • the present invention relates to the treatment of molten iron and systems and compositions therefor.
  • Metal treatment agents are used to modify the composition, morphology and/or distribution of graphite particles found in molten iron.
  • Metal treatment agents applied to molten iron include nodularising agents and inoculants which are used to alter the morphology of iron structure, and thereby produce Ductile Iron (DI) as well as Compacted Graphite Iron (CGI).
  • Inoculants are additives which introduce nuclei into the molten iron to act as crystallisation points for carbon dissolved within the molten iron - these crystallisation points alter the graphite precipitation and structural formation of the casting. Poor inoculation leads to the undesirable formation of iron carbide within the casting as the iron cools.
  • inoculants are mostly alloys based on ferrosilicon as a carrier with additions of “active agents” such as calcium, aluminium, barium, zircon, strontium and rare earth metals.
  • active agents such as calcium, aluminium, barium, zircon, strontium and rare earth metals.
  • the oxygen and/or sulphur contained therein is fully or partially bound to the active agents within the inoculant composition and thus precipitates out as oxides, sulphides or oxysulphides.
  • These sub- microscopic chemical compounds/precipitates act as crystallization nuclei for the precipitation of the graphite particles of the cast iron during solidification.
  • the inoculant compositions themselves are provided as a powder or granular material, with particles with an average size ranging from 0.2mm up to 15mm.
  • the amount of the inoculant composition necessary is very low e.g. a relatively high addition rate of 0.4 to 0.5 wt% of the inoculant composition relative to the weight of the iron being treated is only 4 to 5 kg per tonne of metal.
  • conventional inoculant compositions have a concentration of around 5% of active agents, corresponding to an addition rate of about amount of material to keep costs low.
  • significant problems are found with the mixing of the inoculant through the molten iron.
  • the inoculant may be provided within a ladle prior to the molten iron being poured into the ladle.
  • inoculants are usually based on 90% ferrosilicon, wherein ferrosilicon acts as a soluble carrier i.e. the active component of such a ferrosilicon based inoculant may represent only 10% of the total weight or volume of the inoculant composition.
  • the low concentration of the composition means larger amounts of the composition are required but provides a much greater error tolerance and leads to improved mixing through the melt. However, this increases the cost to produce, transport, and use the inoculant composition.
  • an inoculant composition for treating molten iron.
  • the inoculant composition may comprise 10 to 90 wt% of an active agent.
  • the inoculant composition may comprise 90 to 10 wt% of a carrier.
  • the active agent may comprise one or more of barium, bismuth, manganese, and zirconium as the primary component.
  • the inoculant composition may comprise less than 0.5 wt% of magnesium.
  • the active agent may comprise 3-40 wt% zirconium (relative to the overall weight of the inoculant composition).
  • the active agent comprises 3 to 25 wt% of zirconium.
  • the active agent comprises 4 to 6 wt%, 8 to 15 wt %, 10 to 12 wt %, or 18 to 22 wt% of zirconium.
  • the active agent comprises 25 to 40 wt%, and optionally, 30 to 35 wt%, of zirconium.
  • the active agent may comprise 3-25 wt% bismuth (relative to the overall weight of the inoculant composition).
  • the active agent may comprise at least 4, 5, 6, 7, 8, 9, 10, 12, 14, 15, 16, 18, 20, 22, or 24 wt% of bismuth.
  • the active agent may comprise less than 24, 22, 20, 18, 16, 15, 14, 12, 10, 9, 8, 7, 6, 5, or 4 wt% of bismuth.
  • the active agent comprises 4 to 6 wt %, or 5 to 15 wt% of bismuth.
  • the active agent may comprise 5-40 wt% barium (relative to the overall weight of the inoculant composition).
  • the active agent may comprise at least 22, 24, 25, 26, 28, 30, 32, 34, 35, 36, of 38 wt% of barium.
  • the active agent may comprise at least 6, 7, 8, 9,
  • the active agent may comprise less than 38, 36, 35, 34, 32, 30, 28, 26, 25, 24, 22, 20, 18, 16, 15, 14, 12, 10, 9, 8, 7, or 6 wt% of barium. In some embodiments, the active agent comprises 5 to 15 wt% barium, or 10 to 12 wt% barium. In some further embodiments, the active agent comprises 30 to 40 wt% barium e.g. 34 to 36 wt% or 35wt% barium.
  • the inoculant composition may comprise a secondary active agent and/or a secondary component. In some embodiments, the inoculant composition comprises a plurality of active agents. As noted above, the primary component would be the active agent with the greatest addition rate to the inoculant composition. Secondary active agents thus provide an additional inoculant effect.
  • Secondary components may comprise compound or materials which do not have an inoculant effect and/or which are selected due to other useful properties or effects on the inoculant composition.
  • the active agent may further comprise 0 to 5 wt% of aluminium.
  • the active agent may comprise at least 0.5, 1 , 1.5, 2, 3, or 4 wt% of aluminium.
  • the active agent may comprise less than 4, 3, 2, 1.5, 1, or 0.5 wt% aluminium.
  • the active agent comprises 1 to 2 wt% of aluminium.
  • the active agent may comprise no more than 1.5 wt% of aluminium.
  • the aluminium may be present as a secondary active agent or secondary component.
  • the inoculant composition may comprise 0-22 wt% manganese (relative to the overall weight of the inoculant composition).
  • the inoculant composition may comprise at least 0.2, 0.3, 0.5, 1 , 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 15, 16, 18, or 19 wt% of manganese.
  • the inoculant composition may comprise less than 19, 18, 16, 15, 14, 12, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1.5, 1, 0.5, 0.3, or 0.2 wt% of manganese.
  • the inoculant composition comprises 0.3 to 20 wt %, 0.3 to 15 wt%, or 10 to 12 wt% of manganese.
  • the manganese may be present as a secondary component. Manganese is effective in lowering the melting point of the inoculant composition alloy, thus improving the treatment process.
  • the active agent comprises 8 to 15 wt% of zirconium and 0.3 to 15 wt% of manganese. In a further series of embodiments, the active agent comprises 25 to 40 wt% of zirconium and 0.3 to 20 wt% of manganese. In some embodiments, the active agent comprises no more than 1.5 wt% of aluminium. Alloys of zirconium e.g. with manganese or other metals, are particularly desirable due to the lower solubility of zirconium within molten iron.
  • the active agent comprises 3 to 25 wt% of zirconium and 3 to 25 wt % of bismuth.
  • the active agent may comprise 4 to 6 wt% of zirconium and 4 to 6 wt% of bismuth.
  • the active agent may optionally comprise 0 to 5 wt % of manganese.
  • the active agent may comprise 0 to 5 wt% of aluminium, and optionally, 1 to 2 wt% of aluminium.
  • the active agent comprises 18 to 22 wt% of zirconium and 5 to 15 wt % of bismuth.
  • the active agent may comprise 0 to 22 wt% of manganese.
  • the active agent may comprise 0 to 5 wt% of aluminium, and optionally, 1 to 2 wt% of aluminium.
  • the active agent comprises 20 to 40 wt% of barium and 0 to 10 wt% of calcium. In some embodiments, the active agent comprises 30 to 35 wt% of barium and 1 to 6 wt% of calcium. In some embodiments, the active agent comprises no more than 1.5 wt% of aluminium.
  • the inoculant composition may comprise less than 0.5wt% carbon, less than 0.1 wt% sulphur, and/or less than 0.5wt% phosphorus.
  • the carrier may comprise iron, silicon, and/or ferrosilicon.
  • the carrier may comprise 10 to 70 wt% silicon (relative to the overall weight of the inoculant composition), either as silicon or as ferrosilicon.
  • the carrier may comprise at least 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, or 65 wt% of silicon.
  • the carrier may comprise less than 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, or 15 wt% of silicon.
  • the carrier comprises 10 to 20 wt% of silicon.
  • the carrier comprises 45 to 60 wt% of silicon.
  • the balance of the inoculant composition may comprise iron, either as iron or as ferrosilicon.
  • the carrier comprises 18 to 85 wt% of iron.
  • the carrier may comprise at least 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80 wt% of iron.
  • the carrier may comprise less than 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, or 15 wt% of iron.
  • the carrier comprises 19 to 50 wt% of iron, 30 to 55 wt% of iron, or 24 to 85 wt% of iron.
  • the inoculant composition may be formed as a single alloy comprising all of the components therein.
  • the inoculant composition may comprise particles or grains with the size of 0.2 mm to 12 mm.
  • the inoculant composition may comprise 90% of particles or grains which fall within the range of 0.2mm to 12 mm.
  • the particles size may be 0.2 to 0.7 mm.
  • Such fine particles are desirable for use with in- stream inoculation systems.
  • the particles or grains may comprise 0.2 to 2mm, 2 to 6mm and/or 6 to 12mm.
  • a method for inoculating molten iron may comprise providing an inoculant composition as described herein to a vessel.
  • the method may comprise adding molten iron to the vessel.
  • the vessel may be a transfer ladle.
  • the present invention can inoculate molten iron and provide high quality castings, even at much lower addition rates. By reducing the quantity of inoculant composition necessary to inoculate a melt, significant cost savings can be achieved. Although the inoculant composition itself is more expensive to produce, at the lower addition rates it is more cost effective for the foundry while still maintaining a high quality.
  • the method may comprise stirring the molten iron e.g. using a rotor. In some embodiments, the method may comprise supplying the molten iron with the inoculant composition through a rotor.
  • a method for inoculating molten iron comprising spraying an inoculant composition as described herein into a stream of molten iron.
  • the method may comprise spraying the inoculant composition into a stream of molten metal between a transfer ladle and a mould.
  • a method for producing an inoculant composition as described herein may comprise: reacting silica, iron and carbon in a submerged arc furnace to form ferrosilicon and carbon dioxide, or remelting a ferrosilicon alloy in an induction furnace.
  • the method may comprise adding one or more active agents to the furnace to form an alloyed inoculant composition comprising the carrier and the active agent.
  • the method may comprise cooling and solidifying the inoculant composition.
  • the method may comprise crushing the inoculant composition to produce a granular and/or powdered inoculant composition.
  • the method may comprise crushing the inoculant composition to a particle size and/or grain size of between 0.2mm and 12mm, or within the ranges described previously.
  • the method may comprise removing particles with a size less than 0.2mm.
  • the method may further comprise mixing the granular and/or powdered inoculant composition with a further granular and/or powdered active agent.
  • the method may comprise mixing the granular and/or powdered inoculant composition with a further carrier.
  • the inventors have also surprisingly found that the inoculant composition E5 (when compared with a commercial inoculant product comprising 4% Zr, 3% Mn, 1.2% Ca, 1% Al, and the balance being ferrosilicon (62-69% Si)) improves the performance of castings (e.g. fewer casting defects) with a low cooling rate at a wall thickness of above 50 mm.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Continuous Casting (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)

Abstract

L'invention concerne un additif de traitement de métaux pour le traitement de fer fondu comprenant de 10 à 90 % en poids d'un agent actif et de 90 à 10 % en poids d'un support. L'agent actif comprend un ou plusieurs éléments parmi le baryum, le bismuth et le zirconium en tant que composant primaire, et la composition d'additif comprend moins de 0,5 % en poids de magnésium. L'additif est approprié pour inoculer du fer fondu pendant des processus de coulée.
PCT/EP2024/059311 2023-04-06 2024-04-05 Additif de traitement de métaux Pending WO2024209040A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN202480023663.7A CN120936733A (zh) 2023-04-06 2024-04-05 金属处理添加剂
AU2024243614A AU2024243614A1 (en) 2023-04-06 2024-04-05 Metal treatment additive
MX2025011881A MX2025011881A (es) 2023-04-06 2025-10-03 Aditivo de tratamiento de metal

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP23167084.5A EP4442848A1 (fr) 2023-04-06 2023-04-06 Additif de traitement de métaux et procédé
EP23167084.5 2023-04-06

Publications (1)

Publication Number Publication Date
WO2024209040A1 true WO2024209040A1 (fr) 2024-10-10

Family

ID=85980710

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2024/059311 Pending WO2024209040A1 (fr) 2023-04-06 2024-04-05 Additif de traitement de métaux

Country Status (6)

Country Link
EP (1) EP4442848A1 (fr)
CN (1) CN120936733A (fr)
AU (1) AU2024243614A1 (fr)
MX (1) MX2025011881A (fr)
TW (1) TW202440949A (fr)
WO (1) WO2024209040A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2290273A (en) * 1940-02-07 1942-07-21 Electro Metallurg Co Composition and method for treating cast iron
EP0232042A2 (fr) * 1986-01-21 1987-08-12 Elkem Metals Company Inoculant pour fonte ou fonte ductile
EP0410603A1 (fr) * 1989-07-26 1991-01-30 Foseco International Limited Coulée de la fonte liquide et filtres utilisés
WO2002081758A1 (fr) * 2001-04-04 2002-10-17 Foseco International Limited Agent inoculant ameliore

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2290273A (en) * 1940-02-07 1942-07-21 Electro Metallurg Co Composition and method for treating cast iron
EP0232042A2 (fr) * 1986-01-21 1987-08-12 Elkem Metals Company Inoculant pour fonte ou fonte ductile
EP0410603A1 (fr) * 1989-07-26 1991-01-30 Foseco International Limited Coulée de la fonte liquide et filtres utilisés
WO2002081758A1 (fr) * 2001-04-04 2002-10-17 Foseco International Limited Agent inoculant ameliore

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
AVEKS: "Aveks Technical Data Sheets", 12 December 2019 (2019-12-12), XP093075159, Retrieved from the Internet <URL:chrome-extension://efaidnbmnnnibpcajpcglclefindmkaj/https://www.aveks.com/wp-content/uploads/2019/05/AveksKatalog2019.pdf> *
BAY RICHARDS ET AL: "Mineral Roy Technical Data Sheet", 28 February 2021 (2021-02-28), XP093075156, Retrieved from the Internet <URL:https://www.mineral-loy.co.za/tag/sorelmetal/> [retrieved on 20230821] *
KOCH M: "INOCULATION OF GREY AND DUCTILE IRON", 13 September 2014 (2014-09-13), XP093041249, Retrieved from the Internet <URL:https://ankirosfoundrycongresstr.files.wordpress.com/2014/09/manuscript4.pdf> [retrieved on 20230421] *

Also Published As

Publication number Publication date
TW202440949A (zh) 2024-10-16
MX2025011881A (es) 2025-11-03
AU2024243614A1 (en) 2025-10-16
EP4442848A1 (fr) 2024-10-09
CN120936733A (zh) 2025-11-11

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