US3403090A - Vessel for measuring oxygen content of a molten metal - Google Patents

Vessel for measuring oxygen content of a molten metal Download PDF

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Publication number
US3403090A
US3403090A US453083A US45308365A US3403090A US 3403090 A US3403090 A US 3403090A US 453083 A US453083 A US 453083A US 45308365 A US45308365 A US 45308365A US 3403090 A US3403090 A US 3403090A
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United States
Prior art keywords
vessel
molten metal
standard electrode
electrode
wall
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Expired - Lifetime
Application number
US453083A
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English (en)
Inventor
Tajiri Iichi
Watanabe Siro
Tanaka Noriyuki
Sanbongi Koji
Ohtani Masayasu
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Yawata Iron and Steel Co Ltd
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Yawata Iron and Steel Co Ltd
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/411—Cells and probes with solid electrolytes for investigating or analysing of liquid metals
    • G01N27/4115—Composition or fabrication of the electrodes and coatings thereon, e.g. catalysts
    • G01N27/4117—Reference electrodes or reference mixtures
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/411—Cells and probes with solid electrolytes for investigating or analysing of liquid metals
    • G01N27/4115—Composition or fabrication of the electrodes and coatings thereon, e.g. catalysts

Definitions

  • This invention relates to la vessel for continuously measuring the oxygen content in a molten metal.
  • a method for measuring electrochemically the oxygen content in a molten metal As a method for measuring electrochemically the oxygen content in a molten metal, a method has been known wherein a refractory material is used as an intermediate electrolyte together with Ia standard electrode material for giving a constant oxygen potential to form an electrolytic cell consisting of molten metal, for instance, molten steel-intermediate electroltye-standard electrode and the oxygen content in the molten steel is calculated from the electrtomotive force of the electrolytic cell.
  • the present invention is, in particular, concerned with a vessel for detecting continuously the oxygen potential in a molten metal during an industrial smelting process or others based on the above-mentioned principle.
  • an object of this invention is to provide a molten metal vessel, in the wall of which a standard electrode is inlaid for continuously measuring the oxygen potential of a molten metal in the vessel.
  • FIG. l is a schematic cross-sectional view showing an embodiment of this invention wherein a standard electrode and metallic electrode are inlaid in the bottom of the melting furnace in order to measure the oxygen potential in the molten metal,
  • FIG. 2 is a graph showing the relation between the electromtive force and the analytic value of oxygen in the steel and ythat between the electromotive force measured. by using the melting furnace shown in FIG. 1,
  • FIG. 3 is a schematic cross-sectional view showing another embodiment of-this invention
  • FIGS. 4 and 6 are a schematic cross-sectional view showing an embodiment of applying the system of inlaying the standard electrode shown in FIG. 3 to a molten metal vessel of an industrial scale, respectively, in which FIG. 4 relates to a position of inlaying the detecting means into a 8O ton ladle and FIG. 6 into a 130 ton converter, y
  • FIGS. and 7 are schematic views showing development of the inlaying states shown in FIGS. 4 yand 6, respectively.
  • a standard electrode alone or together with a metallic electrode are inlaid in the side wall or the bot- Y tom wall of the vessel through the wall thereof, whereby the system may be protected from erosion and contamination caused by slags, and various operations in the vessel may be carried out without being infected, which make possible the stable and continuous measurement of the oxygen potential in the molten metal for a long period of time.
  • FIG. 1 is a schematic view of a melting furnace as an embodiment of the vessel according to the present invention, wherein the detecting means of the present invention are inlaid in the bottom wall of a high frequency induction furnace having a melting capacity of 10 kg. whereby the oxygen potential of a molten steel in the furnace can be continuously measured.
  • 1 is an induction coil for heating
  • 2 is a Crucible made of electrocast magnesia
  • 3 is a refractory material layer for heat insulating said crucible and for preventing leakage of molten metal.
  • the standard electrode consists of a refractory shell 4 made of sintered magnesia which is to serve as an intermediate electrolyte, said refractory shell being filled with powered standard electrode material 5, which is to give a constant oxygen potential to the standard electrode, and with a conducting electrode 6, that is, a material which can be a conductive body without disturbing the constant oxygen potential of the standard electrode, said standard electrode being so inlaid in the vessel wall that the one end of said electrode is exposed to the inner surface of the Crucible through said Crucible wall 2 and the other end thereof is connected with a balance-type electron tube automatic recorder 9.
  • 7 is a refractory plug for preventing cutting by melting of a mild steel rod 8 as a metallic electrode and for securing electric and thermal insulation.
  • an advantage of this invention resides in the points that by equipping the detecting means in the bottom of the furnace, the detecing elecrodes can be protected from erosion by molten slag and violent agitating motion of the molten metal, and that the working property of the furnace is much better as compared with a conventional process in which the electrodes are immersed from above in the bath.
  • the standard electrode consisting of the refractory shell 4 of intermediate electrolyte, the standard electrode material 5 and the conducting electrode material 6 is prepared by using sintered magnesia for said refractory shell 4, powered graphite for said material 5, and graphite rod for said material ⁇ 6.
  • sintered magnesia for said refractory shell 4
  • powered graphite for said material 5
  • graphite rod for said material ⁇ 6.
  • other combinations of electrode materials of various kinds are also applicable.
  • an oxide such as magnesia, alumina, silica, zirconia or -beryllia may be adopted.
  • a non-oxidizing material such as graphite or silicon carbide
  • the electrode material 6 a material having high-temperature resistance and which is not denatured in a reducing atmosphere is required, such as graphite, silicon carbide, tungsten, or other metal wire of high melting point.
  • the conditions required for effecting the method of inlaying the standard electrode in the bottom of the furnace as adopted in the example of the present invention are to use an oxide refractory material, such as alumina, magnesia, silica, zirconia, beryllia, or thoria as the intermediate electrolyte, a lowoxygen potential material, such as graphite or silicon carbide as the powdered material for the standard electrode for giving a constant oxygen potential, and a high melting point non-oxidizing material which is not denatured in a reducing atmosphere, such as graphite, tungsten or nickel as the conductor material.
  • an oxide refractory material such as alumina, magnesia, silica, zirconia, beryllia, or thoria
  • a lowoxygen potential material such as graphite or silicon carbide
  • a high melting point non-oxidizing material which is not denatured in a reducing atmosphere such as graphite, tungsten or nickel as the conductor material.
  • FIG. 3 The schematic cross-sectional view of the melting furnace used in the present example is shown in FIG. 3.
  • the materials and purposes of the numerals 1, 2, and 3 in FIG. 3 are the same as in the aforementioned embodiment. but the electrocast magnesia plus 4 is used simultaneously as the intermediate electrolyte and the standard electrode material, and the conductor 5 is made of a platinum electrode.
  • the numeral 6 denotes a refractory plug for preventing cutting by melting of a mild steel rod as the metallic electrode and securing electric and thermal insulating, 7 is a metallic electrode of a mild steel wire material and 8 is a balance-type electron tube automatic recorder.
  • the melting furnace of this embodiment has the advantage that 'since the standard electrode is constructed by a refractory plug, if the erosion of the furnace bottom proceeds to melt the tip of the standard electrode whereby the electrodes lose the function as electrolytic cell, there are no troubles of molten metal leakage owing to the sufiicient durability of the refractory plug as the structural material for the furnace.
  • the measurement of the oxygen potential of the molted steel may be continuously carried out for a long period of time by varying the distance from the inner surface of the furace wall to the tip of the standard electrode in inlaying 'several electrodes of refractory plugs in the wall of the furnace bottom.
  • magnesia, alumina, zirconia, silica, and 4beryllia are suitable for the refractory plug and a high melting point material having a high chemical stability, such as platinum, platinum-rhodium, nickel, etc., is suitable for the conductor material.
  • FIG. 4 is a schematic cross-sectional view of an 80 ton ladle showing the state where the above-mentioned detecting means are equipped in the wall of said ladle
  • FIG. 6 is another schematic cross-sectional view of a 130 ton convertor showing the state Where the 'similar detecting means are equipped in the wall of said convertor.
  • the developments of these are shown in FIG. 5 and FIG. 7, respectively.
  • FIGS. 5 and 7 (a) designates the molten metal side, (b) a refractory layer lining, (c) iron shield, (d) refractory cement, (e) molten erosion line, (f) a switch, an-d (g) an electron tube recorder. Further, (D) in FIGS.
  • the electromotive force may be measured by the arrangement in which a plurality of standard electrodes (B1, B2' B3) is inlaid in the wall of the vessel in advance at various distances from the inner surface of the vessel wall to the tip of each standard electrode, and there is installed a switch which is switched over from B1 to B2 and so on in turns in accordance with the exposure of the tip surface of the electrode when erosion by melting of the vessel wall proceeds.
  • a plurality of standard electrodes B1, B2' B3
  • a molten metal vessel for measuring the oxygen content in a molten metal in the vessel comprising at least one standard electrode consisting of a refractory shell of intermediate electrolyte of an oxide selected from the group consisting of magnesia, zirconia, alumina, silica, beryllia and thoria, said shell being filled with powdered material of low oxygen potential selected from the group consisting of graphite and silicon carbide and a conducting body material selected from the group consisting of graphite, tungsten and nickel, said standard electrode being so inlaid in the vessel wall that one end of said standard electrode is exposed to the inner surface of the vessel through the vessel wall and the other end thereof is connected with a balance-type electron tube automatic recorder.
  • a molten metal vessel according to the claim 1 in which the standard electrode is inlaid together Iwith a metallic electrode made of a substance selected from the group consisting of iron, tungsten and nickel in the vessel wall.
  • a molten metal vessel according to claim 1 in which -a plurality of the standard electrodes is inlaid in the vessel wall at various distances from the inner surface of the vessel wall to the tip of each standard electrode, and a switch is adapted to be switched over in turn from one standard electrode to the other in accordance with erosion by melting of the vessel wall.
  • a molten metal vessel for measuring the oxygen content in a molten metal in the vessel comprising a standard electrode consisting of an intermediate electrolyte shell of an oxide selected from the group consisting of magnesia, zirconia, alumina, silica, beryllia and thoria, a conducting body made of a substance selected from the group consisting of platinum, platinumrhodium, silicon carbide and graphite being inlaid in 5-
  • the standard electrode is inlaid together with a metallic electrode made of a substance selected from the group consisting of iron, tungsten Iand nickel in the vessel wall.
US453083A 1964-05-06 1965-05-04 Vessel for measuring oxygen content of a molten metal Expired - Lifetime US3403090A (en)

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GB (1) GB1111264A (de)

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3454486A (en) * 1966-04-12 1969-07-08 Gkn Group Services Ltd Apparatus for measurement of oxygen potential of gases at high temperatures
US3514377A (en) * 1967-11-27 1970-05-26 Gen Electric Measurement of oxygen-containing gas compositions and apparatus therefor
US3523066A (en) * 1966-06-23 1970-08-04 Atomic Energy Authority Uk Determination of combined carbon in metals
US3619381A (en) * 1968-12-23 1971-11-09 George R Fitterer Determining oxygen content of materials
US3645720A (en) * 1968-08-08 1972-02-29 Nippon Kokan Kk Method of deoxidizing steel
US3674654A (en) * 1970-12-11 1972-07-04 Ford Motor Co Determination of oxygen in molten steel
US3681972A (en) * 1968-09-11 1972-08-08 Salzgitter Huettenwerk Ag Process and device for determining the oxygen concentration in metal melts
US3719574A (en) * 1970-07-06 1973-03-06 Metallurgie Hoboken Apparatus for measuring in a continuous manner the oxygen in a molten metal
US3769189A (en) * 1969-06-13 1973-10-30 Atomic Energy Authority Uk Apparatus for carbon content analysis
JPS4990598A (de) * 1972-12-06 1974-08-29
US3891512A (en) * 1972-12-06 1975-06-24 Ford Motor Co Determination of oxygen in molten steel
US4021326A (en) * 1972-06-02 1977-05-03 Robert Bosch G.M.B.H. Electro-chemical sensor
US4035244A (en) * 1974-11-01 1977-07-12 Mita Industrial Company Limited Electric recording process
US4049524A (en) * 1975-07-08 1977-09-20 Nissan Motor Company, Limited Oxygen sensor with noncatalytic electrode
US4105523A (en) * 1976-03-31 1978-08-08 A. R. F. Products, Inc. Biochemical oxygen demand measuring device
US4174258A (en) * 1978-05-03 1979-11-13 Bendix Autolite Corporation Solid electrolyte oxygen sensor with zero oxygen reference
US4295939A (en) * 1979-03-30 1981-10-20 Hydro-Quebec Method and device for detecting a gaseous anhydride in an oxygen bearing gas
US4485002A (en) * 1982-03-16 1984-11-27 Wuenning Joachim Measuring device for the determination of the activity of carbon in furnace atmospheres
US4526667A (en) * 1984-01-31 1985-07-02 Parkhurst Warren E Corrosion protection anode
US4657641A (en) * 1985-05-15 1987-04-14 Nisshin Steel Co., Ltd. Determination of silicon in molten metal
US4908105A (en) * 1985-02-15 1990-03-13 Hydrolab Corporation Flow-compensated electrochemical cell and method of analysis
US6074547A (en) * 1997-08-21 2000-06-13 Wacker Siltronic Gesellschaft Fur Halbleitermaterialien Ag Process and device for measuring the oxygen potential in a silicon melt

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4140475A (en) * 1976-06-30 1979-02-20 Robertshaw Controls Company Combustion detection apparatus
IT1197738B (it) * 1983-11-04 1988-12-06 Centro Speriment Metallurg Perfezionamento nelle pile ad ossigeno

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3138490A (en) * 1961-02-28 1964-06-23 Gen Electric Fuel cell
US3147149A (en) * 1961-02-27 1964-09-01 Mc Graw Edison Co Fuel cell construction
US3216911A (en) * 1961-09-29 1965-11-09 Union Carbide Corp Method of determining gas concentration and fuel cell construction
US3297551A (en) * 1961-01-09 1967-01-10 Atomic Energy Authority Uk Determination of oxygen in fluids

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3297551A (en) * 1961-01-09 1967-01-10 Atomic Energy Authority Uk Determination of oxygen in fluids
US3147149A (en) * 1961-02-27 1964-09-01 Mc Graw Edison Co Fuel cell construction
US3138490A (en) * 1961-02-28 1964-06-23 Gen Electric Fuel cell
US3216911A (en) * 1961-09-29 1965-11-09 Union Carbide Corp Method of determining gas concentration and fuel cell construction

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3454486A (en) * 1966-04-12 1969-07-08 Gkn Group Services Ltd Apparatus for measurement of oxygen potential of gases at high temperatures
US3523066A (en) * 1966-06-23 1970-08-04 Atomic Energy Authority Uk Determination of combined carbon in metals
US3514377A (en) * 1967-11-27 1970-05-26 Gen Electric Measurement of oxygen-containing gas compositions and apparatus therefor
US3645720A (en) * 1968-08-08 1972-02-29 Nippon Kokan Kk Method of deoxidizing steel
US3681972A (en) * 1968-09-11 1972-08-08 Salzgitter Huettenwerk Ag Process and device for determining the oxygen concentration in metal melts
US3619381A (en) * 1968-12-23 1971-11-09 George R Fitterer Determining oxygen content of materials
US3769189A (en) * 1969-06-13 1973-10-30 Atomic Energy Authority Uk Apparatus for carbon content analysis
US3719574A (en) * 1970-07-06 1973-03-06 Metallurgie Hoboken Apparatus for measuring in a continuous manner the oxygen in a molten metal
US3674654A (en) * 1970-12-11 1972-07-04 Ford Motor Co Determination of oxygen in molten steel
US4021326A (en) * 1972-06-02 1977-05-03 Robert Bosch G.M.B.H. Electro-chemical sensor
JPS4990598A (de) * 1972-12-06 1974-08-29
US3891512A (en) * 1972-12-06 1975-06-24 Ford Motor Co Determination of oxygen in molten steel
JPS5340507B2 (de) * 1972-12-06 1978-10-27
US4035244A (en) * 1974-11-01 1977-07-12 Mita Industrial Company Limited Electric recording process
US4049524A (en) * 1975-07-08 1977-09-20 Nissan Motor Company, Limited Oxygen sensor with noncatalytic electrode
US4105523A (en) * 1976-03-31 1978-08-08 A. R. F. Products, Inc. Biochemical oxygen demand measuring device
US4174258A (en) * 1978-05-03 1979-11-13 Bendix Autolite Corporation Solid electrolyte oxygen sensor with zero oxygen reference
US4295939A (en) * 1979-03-30 1981-10-20 Hydro-Quebec Method and device for detecting a gaseous anhydride in an oxygen bearing gas
US4485002A (en) * 1982-03-16 1984-11-27 Wuenning Joachim Measuring device for the determination of the activity of carbon in furnace atmospheres
US4526667A (en) * 1984-01-31 1985-07-02 Parkhurst Warren E Corrosion protection anode
WO1985003529A1 (en) * 1984-01-31 1985-08-15 Parkhurst Warren E Corrosion protection anode
US4908105A (en) * 1985-02-15 1990-03-13 Hydrolab Corporation Flow-compensated electrochemical cell and method of analysis
US4657641A (en) * 1985-05-15 1987-04-14 Nisshin Steel Co., Ltd. Determination of silicon in molten metal
US4708783A (en) * 1985-05-15 1987-11-24 Nisshin Steel Co., Ltd. Apparatus for the determination of silicon in molten metal
US6074547A (en) * 1997-08-21 2000-06-13 Wacker Siltronic Gesellschaft Fur Halbleitermaterialien Ag Process and device for measuring the oxygen potential in a silicon melt

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GB1111264A (en) 1968-04-24
DE1673336A1 (de) 1970-04-16

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