US3484232A - Method of improving the properties of a ferrous metal in the molten state - Google Patents

Method of improving the properties of a ferrous metal in the molten state Download PDF

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Publication number
US3484232A
US3484232A US581920A US3484232DA US3484232A US 3484232 A US3484232 A US 3484232A US 581920 A US581920 A US 581920A US 3484232D A US3484232D A US 3484232DA US 3484232 A US3484232 A US 3484232A
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United States
Prior art keywords
bath
metal
properties
improving
ferrous metal
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Expired - Lifetime
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US581920A
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English (en)
Inventor
Pierre Yves Karinthi
Etienne Spire
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Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Air Liquide SA
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Priority claimed from FR35745A external-priority patent/FR1463079A/fr
Application filed by Air Liquide SA filed Critical Air Liquide SA
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Publication of US3484232A publication Critical patent/US3484232A/en
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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
    • 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
    • B22D1/002—Treatment with gases
    • B22D1/005—Injection assemblies therefor

Definitions

  • a halogenated compound is brought in liquid phase into contact with a porous device which on its opposite side contacts molten ferrous metal.
  • the halogenated liquid is forced by gas pressure through the porous device and into the molten metal.
  • the halogen may be used to remove unwanted elements from the metal.
  • the nonhalogen part of the compound may combine with elements dissolved in the metal or may itself dissolve in the metal.
  • This invention relates to a method of improving the properties of a steel or a cast iron by treating it in the molten condition.
  • the invention is characterised by the fact that there is injected into the molten metal, in the liquid or vapour state, mixed or not mixed with inert gas, through a permeable wall, a halogenated compound which is forced through said wall by gas pressure and which, having possibly decomposed on contact with the molten metal or in contact with a sumciently hot portion of permeable wall, reacts chemically with the molten metal and improves the properties of the metal obtained, either by modifying its quality, or by modifying its composition.
  • the method of injection which is easy to carry out, imparts great efficiency to the reagents because they are thereby finely distributed in the liquid metal.
  • (B) Fixing the carbon for example by means of titanium trichloride, titanium tetrachloride, zirconium tetrachloride and niobium pentachloride, particularly in stain- 3,484,232 Patented Dec. 16, 1969 less steels, extra-mild steels for sheet intended for enamelling, and in all ferrous metals in which this fixation is beneficial. These reagents react through their metal. It is known that certain ferro-titaniums, notably the conventional composition containing 30% of titanium, are difiicult to dissolve in ferrous metals.
  • the incorporation of small quantities of an alloying ele ment, using a compound which decomposes, has already been proposed.
  • the compound in question was a metal carbonyl which is a costly reagent; furthermore, it would have been poorly utilised because it was proposed to introduce it through a single orifice which would have produced large bubbles.
  • the present invention permits the use of a relatively inexpensive reagent, and permits it to be employed very efiiciently, in contrast to the conventional ferro-alloys, the yields from which are in the order of 60% Generally, the weight of reagent introduced does not exceed 1% of the weight of the metal treated.
  • FIGURE 1 represents the general arrangement of the treatment vessel and of the auxiliary vessel for introducing the reagent
  • FIGURE 2 shows a different embodiment of the same general arrangement
  • FIGURE 3 represents a variant in which the auxiliary vessel is in the form of a plunger tube having a perme. able base;
  • FIGURE 4 shows a variant of the equipment of FIG- URE 2, in which the reagent is vaporized before being introduced.
  • FIGURE 1 there is shown a vessel 1, the base of which is provided with a permeable plug 2.
  • the rear portion of this plug is surrounded by a fluid-tight envelope 3 connected by a pipe 4 to an auxiliary vessel 5 containing the halogenated compound to be forced into the plug.
  • the pipe 4 passes into this vessel through a plunger tube 6.
  • a pipe 7 connects the vessel 5 to a gas cylinder 8, provided with a control valve 9 and a manometer-flowmeter unit 10.
  • the vessel 5 is further provided with a discharge pipe 11 fitted with a valve 12.
  • the vessel 5 can be placed on a balance 13 so as to facilitate the measuring out of the liquid forced via the pipe 4 and control valve 14 through the porous plug.
  • FIGURE 2 represents a variant in which the auxiliary vessel 34 is attached to the treatment vessel 1 and is fixed in alfluid-tight manner beneath the base of this latter vesse A forcer pipe is arranged in the form of a plunger tube 37 directed towards the base of the auxiliary vessel.
  • this latter vessel is provided with a pressurizing pipe 7 connected to a gas cylinder 8, and with a dis charge pipe 11.
  • heating means represented symbolically by an electric coil 15. This could be a resistance or an inductance coil, or could even be replaced by a spiral steam pipe.
  • the halogenated compound can thus be loaded into the auxiliary vessel in the solid condition, then melts when it is to be forced up through the porous plug 2.
  • the halogenated compound could initially be contained, in the solid, liquid, or even gaseous state, in an ampoule or a sealed cartridge fitted with a fusible plug or with a plug which could be broken by a magnetic hammer or any other equivalent means.
  • treatment vessel 1 is provided with a fluidtight cover 16 connected by piping 17 to a vacuum pump (not shown).
  • the injection equipment shown in FIGURE 3 is in the form of a refractory plunger tube 18 closed by a porous plug 19.
  • the tube 18 has in its axis a cavity 20 surrounded by a coil 21 intended to melt the halogenated compound 22 previously introduced in the solid condition into the cavity 20.
  • This cavity is connected by a pipe 23 to a source of inert gas, not illustrated.
  • the tube 18 is plunged into the bath of metal to be treated, in such manner that its porous mouthpiece 19 is located below the surface 24 of the bath.
  • FIGURE 4 shows a variation of equipment of FIG- URE 2 in which the auxiliary vessel 34 is provided, at its base, with a porous plug fitted with a fluid-tight envelope 26 connected to a gas pipe 7.
  • This vessel is optionally provided with a heating coil 15.
  • the bubbling of gas through the plug 25 and then through the halogenated reagent brought to the region of its boiling point entrains a certain quantity of this reagent in the diluted vapour state.
  • This diluted vapour, together with the gas enters the metal bath through the permeable element 2 which separates the treatment vessel 1 and the auxiliary vessel 34. In this manner, the reagent passes into the metal to be treated, forcing through a fluid-permeable wall pressure at the temperature obtaining in the auxiliary vessel.
  • a method for improving the properties of a ferrous metal comprising establishing a bath of molten ferrous metal to be treated, forcing through a fluid-permeable wall and into the bath a halogen-containing fluid that is chemically reactive with at least one component of the bath, the halogen of said fluid being present in the form of a halogenated compound selected from the class consisting of halogenated hydrocarbons and lead dichloride, said bath containing manganese to be at least partially eliminated by said halogenated compound, and recovering manganese from fumes evolved from the bath.
  • a method for improving the properties of a ferrous metal comprising establishing a bath of molten ferrous metal to be treated, and forcing through a fluid-permeable wall and into the bath a halogen-containing fluid that is chemically reactive with at least one component of the bath, said halogen of said fluid being present in the form of a halogenated compound selected from the class consisting of titanium trichloride, titanium tetrachloride, zirconium trichloride, and niobium pentachloride, said bath containing carbon to be fixed by said halogenated compound.
  • a method for improving the properties of a ferrous metal comprising establishing a bath of molten ferrous metal to be treated, and forcing through a fluidpermeable wall and into the bath a halogen-containing fluid that is chemically reactive with at least one con? ponent of the bath; the improvement comprising bringing said halogen-containing fluid into contact with said fluidpermeable wall as a liquid under pressure.
  • halogen of said fluid being present in the form of a halogenated compound the nonhalogen part of which remains in the bath.
  • ferrous metal being carbon steel and the halogen of said fluid being present in the form of a halogenated compound the nonhalogen part of which refines the grain of the steel.
  • the halogen of said fluid being present in the form of a halogen compound whose decomposition temperature is lower than the temperature of the bath.
  • the halogen of said fluid being present in the form of a compound whose decomposition temperature is lower than the temperature of at least a portion of said wall.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Crucibles And Fluidized-Bed Furnaces (AREA)
US581920A 1965-10-21 1966-09-26 Method of improving the properties of a ferrous metal in the molten state Expired - Lifetime US3484232A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR35745A FR1463079A (fr) 1965-10-21 1965-10-21 Procédé de traitement des métaux liquides, applicable notamment à l'élaboration de fonte nodulaire
FR72625A FR90350E (fr) 1965-10-21 1966-08-10 Procédé de traitement des métaux liquides, applicable notamment à l'élaboration de fonte nodulaire
US86030769A 1969-09-23 1969-09-23

Publications (1)

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US3484232A true US3484232A (en) 1969-12-16

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US581920A Expired - Lifetime US3484232A (en) 1965-10-21 1966-09-26 Method of improving the properties of a ferrous metal in the molten state
US860307A Expired - Lifetime US3640702A (en) 1965-10-21 1969-09-23 Method of improving the properties of a ferrous metal in the molten state

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US860307A Expired - Lifetime US3640702A (en) 1965-10-21 1969-09-23 Method of improving the properties of a ferrous metal in the molten state

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US (2) US3484232A (sv)
BE (1) BE688468A (sv)
DE (1) DE1508113B1 (sv)
FR (1) FR90350E (sv)
GB (1) GB1131570A (sv)
SE (1) SE309788B (sv)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3926623A (en) * 1972-12-20 1975-12-16 Interlake Inc Process for purification of manganese alloys
US4006013A (en) * 1972-12-28 1977-02-01 Outokumpu Oy Process for fining carbonaceous alloys of iron, nickel and/or cobalt
US4026698A (en) * 1975-09-18 1977-05-31 Urban Reclamation Technologies, Inc. Removal of tin from molten iron by chlorination, using oxygen to conserve chlorine and to produce tin oxide
US4415358A (en) * 1981-04-24 1983-11-15 Arbed S.A. Method of desulfurizing a ferrous melt
US4421555A (en) * 1981-03-23 1983-12-20 Arbed S.A. Method of and apparatus for metallurgical treatment of a melt
US4636249A (en) * 1984-12-28 1987-01-13 British Steel Corporation Treatment of molten metal
US4770697A (en) * 1986-10-30 1988-09-13 Air Products And Chemicals, Inc. Blanketing atmosphere for molten aluminum-lithium alloys or pure lithium
US5091000A (en) * 1987-12-25 1992-02-25 Nkk Corporation Method for cleaning molten metal and apparatus therefor
EP0535386A1 (de) * 1991-10-01 1993-04-07 Messer Griesheim Gmbh Verfahren zur Herstellung von Basiseisen für Sphäroguss
US6228187B1 (en) 1998-08-19 2001-05-08 Air Liquide America Corp. Apparatus and methods for generating an artificial atmosphere for the heat treating of materials
US6487905B2 (en) * 2000-04-28 2002-12-03 Nissei Plastic Industrial Co., Ltd. Method and apparatus for detecting molten metal level in container for melting metallic material
US6491863B2 (en) 2000-12-12 2002-12-10 L'air Liquide-Societe' Anonyme A' Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes George Claude Method and apparatus for efficient utilization of a cryogen for inert cover in metals melting furnaces
US20080182022A1 (en) * 2006-09-27 2008-07-31 La Sorda Terence D Production of an Inert Blanket in a Furnace
US20090064821A1 (en) * 2006-08-23 2009-03-12 Air Liquide Industrial U.S. Lp Vapor-Reinforced Expanding Volume of Gas to Minimize the Contamination of Products Treated in a Melting Furnace
US20090288520A1 (en) * 2006-08-23 2009-11-26 Air Liquide Industrial U.S. Lp Vapor-Reinforced Expanding Volume Of Gas To Minimize The Contamination Of Products Treated In A Melting Furnace
US20140341493A1 (en) * 2011-07-08 2014-11-20 Thyssenkrupp Steel Europe Ag Device for reducing pressure in hollow bodies in media at higher temperatures

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2187919B1 (sv) * 1972-06-15 1974-10-25 Bonvarite
FI50997C (sv) * 1972-12-28 1976-09-10 Outokumpu Oy Raffineringsförfarande för kolhaltiga järn-, nickel- och koboltkomposi tioner.
DE2820555A1 (de) * 1978-05-11 1979-11-15 Basf Ag Verfahren zur behandlung von roheisen- und stahlschmelzen bzw. legierungen
US4221366A (en) * 1979-01-23 1980-09-09 Hylsa, S.A. Gas distributing closure plug for metallurgical reactor
US4490172A (en) * 1979-06-29 1984-12-25 Moore William H Method of melting and refining steel and other ferrous alloys
US4409028A (en) * 1979-10-24 1983-10-11 Moore William H Process for producing cast iron
FR2491954A1 (fr) * 1980-10-14 1982-04-16 Pechiney Aluminium Dispositif de traitement d'un bain de metal liquide par injection de gaz
FR2501722B1 (fr) * 1981-03-11 1986-08-14 Siderurgie Fse Inst Rech Procede de brassage pneumatique d'un bain metallique
EP0544967B1 (de) * 1991-11-28 1995-06-14 Carbagas Verfahren zur Unterdrückung von Staub und Rauch bei der Elektrostahlherstellung

Citations (8)

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Publication number Priority date Publication date Assignee Title
GB977105A (sv) * 1960-02-29 1900-01-01
US2134905A (en) * 1937-01-30 1938-11-01 British & Dominions Feralloy L Manufacture of cast iron
FR1146218A (fr) * 1955-09-19 1957-11-07 Patentverwertung Ag Procédé et dispositif de fabrication de pièces coulées
US2871008A (en) * 1950-11-02 1959-01-27 Air Liquide Apparatus for gas flushing of molten metal
CA590537A (en) * 1960-01-12 Cohen De Lara Georges Introduction of a gas in the treatment of a molten metal
CA619017A (en) * 1961-04-25 H. Brennan Joseph Purification of silicon alloys
GB999481A (en) * 1960-12-07 1965-07-28 Expl Des Procedes Chimique Et Improvements in pumps having reciprocating piston which acts as a rotary distributor
CA739408A (en) * 1966-07-26 Verge Jacques Method and apparatus for purging molten metal of gaseous impurities

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB357539A (en) * 1930-06-19 1931-09-21 May & Baker Ltd Improvements relating to the manufacture of metals and alloys
DE967617C (de) * 1948-12-02 1957-11-28 Erwin Holweg Dr Ing Gasmetallurgisches Verfahren zur Verbesserung von Metallschmelzen, insbesondere von Stahl- und Gusseisenschmelzen
DE1236540B (de) * 1952-08-04 1967-03-16 Gutehoffnungshuette Sterkrade Vorrichtung zur Behandlung von fluessigem Eisen oder sonstigen Schmelzen
DE969984C (de) * 1953-06-23 1958-08-07 Gutehoffnungshuette Sterkrade Vorrichtung zum Behandeln von Metallschmelzen
CH341949A (de) * 1955-09-19 1959-10-31 Patentverwertung Ag Verfahren und Vorrichtung zur Herstellung von Gussstücken
DE1061350B (de) * 1955-10-06 1959-07-16 Rheinstahl Eisenwerke Gelsenki Verfahren zur Herstellung von schwefelreichem Gusseisen mit kugelfoermiger Graphitausbildung
US2826494A (en) * 1955-12-27 1958-03-11 Ohio Commw Eng Co Process for making alloys
DE1019674B (de) * 1956-07-06 1957-11-21 Ruhrstahl Ag Emaillierbare Staehle mit niedrigem Kohlenstoffgehalt und hoher Festigkeit
DE1025630B (de) * 1956-09-19 1958-03-06 Conradty Fa C Vorrichtung zum Einleiten von Gasen in Metall- oder sonstige Schmelzen
GB869953A (en) * 1957-02-27 1961-06-07 Ruhrstahl Ag Improvements in or relating to the refining of steel
CH394264A (de) * 1960-10-07 1965-06-30 Bochumer Verein Fuer Gussstahl Verfahren zum Entgasen und Vergiessen von Schmelzen und Vorrichtung zur Durchführung des Verfahrens
DE1177183B (de) * 1960-12-01 1964-09-03 Rheinstahl Huettenwerke Ag Verfahren zur Reinigung von unlegierten und legierten Staehlen
GB960038A (en) * 1962-05-29 1964-06-10 Norman David Weiss Treatment of molten metals

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA590537A (en) * 1960-01-12 Cohen De Lara Georges Introduction of a gas in the treatment of a molten metal
CA619017A (en) * 1961-04-25 H. Brennan Joseph Purification of silicon alloys
CA739408A (en) * 1966-07-26 Verge Jacques Method and apparatus for purging molten metal of gaseous impurities
US2134905A (en) * 1937-01-30 1938-11-01 British & Dominions Feralloy L Manufacture of cast iron
US2871008A (en) * 1950-11-02 1959-01-27 Air Liquide Apparatus for gas flushing of molten metal
FR1146218A (fr) * 1955-09-19 1957-11-07 Patentverwertung Ag Procédé et dispositif de fabrication de pièces coulées
GB977105A (sv) * 1960-02-29 1900-01-01
GB999481A (en) * 1960-12-07 1965-07-28 Expl Des Procedes Chimique Et Improvements in pumps having reciprocating piston which acts as a rotary distributor

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3926623A (en) * 1972-12-20 1975-12-16 Interlake Inc Process for purification of manganese alloys
US4006013A (en) * 1972-12-28 1977-02-01 Outokumpu Oy Process for fining carbonaceous alloys of iron, nickel and/or cobalt
US4026698A (en) * 1975-09-18 1977-05-31 Urban Reclamation Technologies, Inc. Removal of tin from molten iron by chlorination, using oxygen to conserve chlorine and to produce tin oxide
US4421555A (en) * 1981-03-23 1983-12-20 Arbed S.A. Method of and apparatus for metallurgical treatment of a melt
US4415358A (en) * 1981-04-24 1983-11-15 Arbed S.A. Method of desulfurizing a ferrous melt
US4636249A (en) * 1984-12-28 1987-01-13 British Steel Corporation Treatment of molten metal
US4770697A (en) * 1986-10-30 1988-09-13 Air Products And Chemicals, Inc. Blanketing atmosphere for molten aluminum-lithium alloys or pure lithium
US5091000A (en) * 1987-12-25 1992-02-25 Nkk Corporation Method for cleaning molten metal and apparatus therefor
EP0535386A1 (de) * 1991-10-01 1993-04-07 Messer Griesheim Gmbh Verfahren zur Herstellung von Basiseisen für Sphäroguss
US6508976B2 (en) 1998-08-19 2003-01-21 L'air Liquide-Societe' Anonyme A' Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude Apparatus for generating an artificial atmosphere for the heat treating of materials
US6228187B1 (en) 1998-08-19 2001-05-08 Air Liquide America Corp. Apparatus and methods for generating an artificial atmosphere for the heat treating of materials
US6487905B2 (en) * 2000-04-28 2002-12-03 Nissei Plastic Industrial Co., Ltd. Method and apparatus for detecting molten metal level in container for melting metallic material
US6491863B2 (en) 2000-12-12 2002-12-10 L'air Liquide-Societe' Anonyme A' Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes George Claude Method and apparatus for efficient utilization of a cryogen for inert cover in metals melting furnaces
US20090064821A1 (en) * 2006-08-23 2009-03-12 Air Liquide Industrial U.S. Lp Vapor-Reinforced Expanding Volume of Gas to Minimize the Contamination of Products Treated in a Melting Furnace
US20090288520A1 (en) * 2006-08-23 2009-11-26 Air Liquide Industrial U.S. Lp Vapor-Reinforced Expanding Volume Of Gas To Minimize The Contamination Of Products Treated In A Melting Furnace
US8568654B2 (en) 2006-08-23 2013-10-29 Air Liquide Industrial U.S. Lp Vapor-reinforced expanding volume of gas to minimize the contamination of products treated in a melting furnace
US9267187B2 (en) 2006-08-23 2016-02-23 Air Liquide Industrial U.S. Lp Vapor-reinforced expanding volume of gas to minimize the contamination of products treated in a melting furnace
US20080182022A1 (en) * 2006-09-27 2008-07-31 La Sorda Terence D Production of an Inert Blanket in a Furnace
US8403187B2 (en) 2006-09-27 2013-03-26 Air Liquide Industrial U.S. Lp Production of an inert blanket in a furnace
US20140341493A1 (en) * 2011-07-08 2014-11-20 Thyssenkrupp Steel Europe Ag Device for reducing pressure in hollow bodies in media at higher temperatures
US9683598B2 (en) * 2011-07-08 2017-06-20 Thyssenkrupp Steel Europe Ag Device for reducing pressure in hollow bodies in media at higher temperatures

Also Published As

Publication number Publication date
SE309788B (sv) 1969-04-08
GB1131570A (en) 1968-10-23
US3640702A (en) 1972-02-08
FR90350E (fr) 1967-11-24
BE688468A (sv) 1967-04-19
DE1508113B1 (de) 1970-05-27

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