US3661749A - Apparatus for measuring in a continuous manner the oxygen in a molten metal - Google Patents

Apparatus for measuring in a continuous manner the oxygen in a molten metal Download PDF

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Publication number
US3661749A
US3661749A US794335*A US3661749DA US3661749A US 3661749 A US3661749 A US 3661749A US 3661749D A US3661749D A US 3661749DA US 3661749 A US3661749 A US 3661749A
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United States
Prior art keywords
metal
tube
tested
electrolyte tube
oxygen
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Expired - Lifetime
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US794335*A
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English (en)
Inventor
Frederick Denys Richardson
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Societe Generale Metallurgique de Hoboken SA
Rst International Metals Ltd
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Societe Generale Metallurgique de Hoboken SA
Rst International Metals 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
    • G01N27/4118—Means for protecting the electrolyte or the electrodes

Definitions

  • ABSTRACT Apparatus for the continuous measurement of oxygen contained in a molten metal which comprises a. a solid oxygen electrolyte tube;
  • insulating means to protect the solid oxygen electrolyte tube against chemical attacks. thermal shocks and mechanical stress due to the contact with the liquid molten metal.
  • the insulating means is a tube made ofa metal containing substance having a high resistance to mechanical stress. to thermal shocks, to chemical attack, to splashing ofthe metal which is to be tested and to the slag of the metal which is to be tested. in addition the insulating means closely surrounds the solid oxygen electrolyte tube and is open at the bottom so that the outer surface of the tube can be directly contacted with the molten metal which is to be tested.
  • the present invention relates more particularly to an immersion device which serves to detect in an electromechanical manner the oxygen potential in the molten metal, and to means for measuring and converting the said potential into ox ygen percentage.
  • One face of the said solid electrolyte is in contact with the metal, for instance with liquid copper containing oxygen in solution, the concentration of which is to be measured and in which a collector of current made of refractory metal is immersed.
  • the other face is placed in contact with a reference electrode working with a known oxygen pressure, for instance with the known mixture Ni-NiO or with an appropriate gas mixture, and connected with another collector of current formed for instance ofa platinum wire.
  • the said voltage is measured by an electrometer the impedance of which is sufficiently high, relative to that of the measuring cell.
  • the present invention consists in a process and apparatus for the measurement in a continuous manner of the oxygen contained in a molten metal such as copper or lead, for detect ing in an electrochemical manner the oxygen potential of the molten metal, comprising means for measuring the electrical potential developed between the two faces of a solid electrolyte which are placed in contact with phases the partial oxygen pressures of which are different from each other, characterized by the use of a tube of high resistance to mechanical and thermal shock, to chemical attack, to splashing by the metal being treated, and to attack by the slag on the metal being treated, which tube surrounds the solid electrolyte and forms a contact electrode with the molten metal,
  • a block of copper or other metal substance which is of low melting point may be arranged below and/or around the solid electrolyte in such a manner that the metal block shall be placed in contact with the bath and shall absorb heat by melting, whilst permitting a progressive heating of the electrolyte.
  • metals or refractory alloys or cermets may be cited, for instance ferritic steel, iron, kanthal or the cermet Cr Ano,
  • Use may be made of a reference electrode consisting of a current of air of constant flow, which is continuously renewed to ensure a constant value of the content of oxygen.
  • the various elements of the apparatus are arranged co-axially in a particularly simple and compact manner as one strong unit, easy to handle.
  • FIG. 1 is a view showing the structure of the clipping or immersion apparatus.
  • FIG. 2 is a view showing another mode of construction of the clipping or immersion apparatus.
  • FIG. 3 is a view showing the dipping or immersion apparatus adapted to a casting ladle for copper.
  • an elongated cup or tube 2 closed at one end, made from the solid electrolyte is fixed by means of a refractory cement 4 to a sheath 3 made of a refractory material (metal, alloy, cermet)which is conducting of electrical current and is highly resistant to chemical and mechanical actions.
  • the end of the tube 2 is placed in contact with a molten bath 1, the contents of oxygen of which are to be measured.
  • the sheath 3 forms one of the current conductors serving for the electrical measurements. This allows of instantaneously making said electrical measurements and of obtaining a compact and strong unit device, easy to handle.
  • the sheath 3 may, for those parts which are not exposed to chemical actions, be prolonged by a portion 17 made of ordinary stainless steelv
  • An injection conduit 5 made of refractory material and nonconductor of current, for instance of aluminous refractory material, extends inside the sheath 3 as near to the bottom of the electrolyte tube as possible, to sweep air at the point of the electrical contact with the bottom of the tube 2 as shown by the arrows 15 in the drawing.
  • the end of the sheath 3 may advantageously be shaped so as to have a tongue which extends 4 to 5 centimeters beyond the solid electrolyte 2, so as to reduce thermal shock when immersed.
  • the tip can be dipped into the metal and held there for some time prior to immersing the electrolyte.
  • the tube 2, the sheath 3, the cement 4, are made as shown in FIG. 1.
  • a block of copper 8 may be placed below the solid electrolyte 2 in contact with the molten metal bath 1 to reduce the effect of ther mal shocks upon the electrolyte 2 which is fragile and protect the electrolyte from slag when immersed.
  • the said block is fixed to the sheath 3 by means of a screw 19, made for instance of steel.
  • a longitudinal channel 18 is advantageously bored in the block of copper 8, permitting the escape of the gases held between the capsule and the block of copper.
  • cooling fluid passes through a device 10 for cooling the head of the apparatus in the direction of the arrows 16 for protecting the head of the apparatus against the effects of flames or of a high thermal radiation.
  • the current collector may be formed by an injection tube which may be made of the same material as the sheath 3, for instance of a refractory material, and which is connected to a metal conductor 12.
  • the lower end of the injection tube 5 (FIG. 2), through which air is blown to renew the oxygen against the wall of the electrolyte, may be cut obliquely so that the tube 5 may be introduced into the liquid silver, whilst allowing the air current l5 to escape above the silver 11, thus avoiding bubbling, which would be produced if air would be allowed to escape after having passed through the silver.
  • the current is thus led through the silver 11 and through the tube 5 for the injection of air, and that tube is preferably made of a refractory material, good conductor of current, for instance of stainless steel, and is connnected with the voltmetre (not shown) by a metal conductor 12.
  • the tube 2 is made of zirconia (ZrO,) fully or partially stabilized by CaO, Y, O, or MgO.
  • ZrO zirconia
  • the sheath 3 when used for copper, it may be made of a current conductor cermet, for instance of Cr AI,O,, or of refractory steel, for instance ferritic steel containing chrome, or an alloy such as kanthal which contains iron and aluminum, in the case of lead, use will preferably be made of an iron sheath.
  • a current conductor cermet for instance of Cr AI,O, or of refractory steel, for instance ferritic steel containing chrome, or an alloy such as kanthal which contains iron and aluminum, in the case of lead, use will preferably be made of an iron sheath.
  • the cement 4 forming the joint between the sheath 3 and the tube 2 may be made of an aluminous cement, such as a mixture of alumina with sodium silicate solution.
  • a refractory ring 14 may advantageously be inserted between the sheath 3 and the tube 2, in order to help in fitting the tubes together and to reduce the thickness of the joint to be filled with cement 4.
  • a refractory fibrous material may be used between the two tubes. A better fit and a better resistance to penetration by liquid metal of the space between the sheath 3 and the tube 2, are obtained.
  • the reference numeral shows the immersion apparatus, which is fixed to a wall 21 of a casting ladle 22 of launder through which the metal is flowing (not illustrated).
  • Apparatus for the continuous measurement by immersion of oxygen contained in a molten metal which comprises:
  • a refractory ring closely surrounding the sides of said electrolyte tube to provide resistance to penetration by the molten metal which is to be tested;
  • insulating means to protect said solid oxygen electrolyte tube against chemical attacks, thermal shocks and mechanical stress due to contact with the liquid molten metal
  • said insulating means being an electrically conducting tube made of a metal containing substance selected from the group consisting of metal and cermet and having a high resistance to mechanical stress, to thermal shocks, to chemical attack, to splashing of the metal which is to be tested and to the slag of the metal which is to be tested;
  • said insulating means closely surrounding said refractory ring and being open at the bottom so that the outer surface of said electrolyte tube can be directly contacted with the molten metal which is to be tested;
  • said insulating means further being adapted to form a contact electrode with the molten metal
  • said refractory ring is joined to said solid oxygen electrolyte tube and to said insulating means by a refractory cement.
  • Apparatus as claimed in claim 1 characterized in that a block of metal material, which is of low melting point, is provided below the solid electrolyte, the block of metal being placed in contact with the bath and being capable of absorbing heat when it melts, to permit a progressive heating of the electrolyte.
  • Apparatus as claimed in claim 2 characterized in that a channel of small diameter is provided in the block of metal material, of low melting point, permitting the escape of gases present between the electrolyte tube and the block of metal material of low melting point.
  • said reference electrode consists of a metal and a constant flow of air which is continuously renewed in order to insure a constant percentage and wherein said reference electrode is located inside said solid electrolyte tube.
  • the apparatus of claim I which includes an injection means located inside the insulating means and inside the solid oxygen electrolyte tube and extending as near to the closed bottom of the electrolyte tube as possible in order to conduct air to the point of electrical contact with the closed bottom of said solid oxygen electrolyte tube; and wherein said injection means is made of a material which is refractory and which is a non-conductor.
  • said solid oxygen electrolyte tube is a solid electrolyte tube of zirconia partially stabilized with a member selected from the group consisting of Y,O CaO, and MgO.
  • said insulating means is made of a material selected from the group of Cr M 0 ferritic steel containing chrome, kanthal alloy, and iron.
  • Apparatus for the continuous measurement by immersion of oxygen contained in a molten metal which comprises:
  • insulating means to protect said solid oxygen electrolyte tube against chemical attacks, thermal shocks and mechanical stress due to contact with the liquid molten metal
  • said insulating means being an electrically conducting tube made of a metal containing substance selected from the group consisting of metal and cermet and having a high resistance to mechanical stress, the thermal shocks, to chemical attacks, to splashing of the metal which is to be tested and to the slag of the metal which is to be tested;
  • said insulating means being open at the bottom so that the outer surface of said electrolyte tube can be directly contacted with the molten metal which is to be tested;
  • said insulating means further being adapted to form a contact electrode with the molten metal
  • said insulating means has a tongue which extends 4 to 5 centimeters beyond said oxygen electrolyte tube.
  • Apparatus as claimed in claim 11 characterized in that a block of metal material, which is of low melting point, is provided below the solid electrolyte, the block of metal being placed in contact with the bath and being capable of absorbing heat when it melts, to permit a progressive heating of the electrolyte.
  • Apparatus as claimed in claim 12 characterized in that a channel of small diameter is provided in the block of metal material, of low melting point, permitting the escape of gases present between the electrolyte tube and the block of metal material of low melting point.
  • said reference electrode consists of a metal and a constant flow of air which is continuously renewed in order to insure a constant percentage 0,; and wherein said reference electrode is located inside said solid electrolyte tube.
  • Apparatus for the continuous measurement by immersion of oxygen contained in a molten metal which comprises:
  • the outer surface of said tube being adapted to be contacted with the molten metal which is to be tested; d. means for measuring the electrochemical potential said insulating means being an electrically conducting tube made of a metal containing substance selected from the group consisting of metal and cermet and having a high resistance to mechanical stress, to thermal shocks. to chemical attacks, to splashing of the metal which is to be tested and to the slag of the metal which is to be tested;
  • said insulating means being open at the bottom so that the outer surface of said electrolyte tube can be directly contacted with the molten metal which is to be tested;
  • said insulating means further being adapted to form a contact electrode with the molten metal
  • a layer of silver provided in said solid electrolyte tube forming a contact between said reference electrode and said means for measuring.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Molecular Biology (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Measuring Oxygen Concentration In Cells (AREA)
  • Investigating And Analyzing Materials By Characteristic Methods (AREA)
US794335*A 1968-02-09 1969-01-27 Apparatus for measuring in a continuous manner the oxygen in a molten metal Expired - Lifetime US3661749A (en)

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Application Number Priority Date Filing Date Title
LU55448 1968-02-09

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US (1) US3661749A (it)
JP (1) JPS5527300B1 (it)
DE (1) DE1906388C3 (it)
FI (1) FI53174C (it)
FR (1) FR1601200A (it)
GB (1) GB1235091A (it)
LU (1) LU55448A1 (it)
SE (1) SE377501B (it)
YU (1) YU36229B (it)
ZM (1) ZM1269A1 (it)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3864231A (en) * 1972-01-31 1975-02-04 Metallurgie Hoboken Apparatus for measuring in a continuous manner oxygen in a molten metal
JPS5141596A (it) * 1974-08-02 1976-04-07 Noranda Mines Ltd
US4105524A (en) * 1974-04-17 1978-08-08 Nissan Motor Company, Limited Oxygen concentration sensor for heated gaseous mixture
FR2408833A1 (fr) * 1977-11-10 1979-06-08 Corning Glass Works Structure de montage pour detecteur d'oxygene
US4166019A (en) * 1975-09-26 1979-08-28 General Electric Company Electrochemical oxygen meter
EP0059222A1 (en) * 1980-09-05 1982-09-08 Nippon Kokan Kabushiki Kaisha Oxygen level sensor for molten metal
US5360269A (en) * 1989-05-10 1994-11-01 Tokyo Kogyo Kabushiki Kaisha Immersion-type temperature measuring apparatus using thermocouple

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2422162A1 (fr) * 1978-04-06 1979-11-02 Electro Nite Perfectionnements aux dispositifs de mesure de la teneur en oxygene actif de bains de metaux en fusion
DE3022189C2 (de) * 1980-06-13 1982-03-18 Fried. Krupp Gmbh, 4300 Essen Anordnung zur kontinuierlichen, elektrochemischen Langzeitmessung des Sauerstoffpotentials und der Temperatur in einem Bad
JPS6152682U (it) * 1984-09-10 1986-04-09
JPS6371092A (ja) * 1986-09-10 1988-03-31 住友重機械工業株式会社 パイプ吊具
JPH06218203A (ja) * 1993-01-28 1994-08-09 Mitsubishi Electric Corp 濾過装置
DE4407217C2 (de) * 1994-03-06 1996-07-04 Erwin Dipl Chem Dr I Thomanetz Vorrichtung zur schnellen analytischen Durchmusterung und dreidimensionalen Kartierung von ruhenden Haufwerken fester und pastöser Stoffe
JP2014160006A (ja) * 2013-02-19 2014-09-04 Tokyo Yogyo Co Ltd センサプローブ

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3347767A (en) * 1963-05-10 1967-10-17 Westinghouse Electric Corp Device for monitoring oxygen content of gases
US3464008A (en) * 1966-10-19 1969-08-26 Siderurgie Fse Inst Rech Device for continuously measuring the oxygen content of a molten metal including an electrolytic cell having a solid electrolyte
US3481855A (en) * 1966-07-15 1969-12-02 United Nuclear Corp Continuous oxygen monitor for liquid metals

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3347767A (en) * 1963-05-10 1967-10-17 Westinghouse Electric Corp Device for monitoring oxygen content of gases
US3481855A (en) * 1966-07-15 1969-12-02 United Nuclear Corp Continuous oxygen monitor for liquid metals
US3464008A (en) * 1966-10-19 1969-08-26 Siderurgie Fse Inst Rech Device for continuously measuring the oxygen content of a molten metal including an electrolytic cell having a solid electrolyte

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
G. R. Fitterer, Journal of Metals, Reprint pp. 1 6, August 1966 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3864231A (en) * 1972-01-31 1975-02-04 Metallurgie Hoboken Apparatus for measuring in a continuous manner oxygen in a molten metal
US4105524A (en) * 1974-04-17 1978-08-08 Nissan Motor Company, Limited Oxygen concentration sensor for heated gaseous mixture
JPS5141596A (it) * 1974-08-02 1976-04-07 Noranda Mines Ltd
US4003814A (en) * 1974-08-02 1977-01-18 Noranda Mines Limited Apparatus for the continuous measurement of the oxygen content of molten copper or alloys thereof
US4166019A (en) * 1975-09-26 1979-08-28 General Electric Company Electrochemical oxygen meter
FR2408833A1 (fr) * 1977-11-10 1979-06-08 Corning Glass Works Structure de montage pour detecteur d'oxygene
US4198279A (en) * 1977-11-10 1980-04-15 Corning Glass Works Oxygen sensor mounting structure
EP0059222A1 (en) * 1980-09-05 1982-09-08 Nippon Kokan Kabushiki Kaisha Oxygen level sensor for molten metal
EP0059222A4 (en) * 1980-09-05 1983-01-14 Nippon Kokan Kk DETECTOR OF THE OXYGEN CONTENT OF A LIQUID METAL.
US5360269A (en) * 1989-05-10 1994-11-01 Tokyo Kogyo Kabushiki Kaisha Immersion-type temperature measuring apparatus using thermocouple

Also Published As

Publication number Publication date
YU36229B (en) 1982-02-25
ZM1269A1 (en) 1969-07-17
DE1906388A1 (de) 1970-04-23
FI53174B (it) 1977-10-31
YU22669A (en) 1981-06-30
DE1906388C3 (de) 1978-08-31
SE377501B (it) 1975-07-07
FR1601200A (it) 1970-08-10
DE1906388B2 (de) 1977-12-22
FI53174C (it) 1978-02-10
LU55448A1 (it) 1969-09-23
GB1235091A (en) 1971-06-09
JPS5527300B1 (it) 1980-07-19

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