US3864231A - Apparatus for measuring in a continuous manner oxygen in a molten metal - Google Patents

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

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Publication number
US3864231A
US3864231A US323493A US32349373A US3864231A US 3864231 A US3864231 A US 3864231A US 323493 A US323493 A US 323493A US 32349373 A US32349373 A US 32349373A US 3864231 A US3864231 A US 3864231A
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United States
Prior art keywords
liquid metal
solid electrolyte
metal
cell
outer tube
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Expired - Lifetime
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US323493A
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English (en)
Inventor
Frederick Denys Richardson
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Societe Generale Metallurgique de Hoboken SA
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Societe Generale Metallurgique de Hoboken SA
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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

  • a known apparatus for the measurement in a continuous manner of the oxygen contained in a molten metal, such as copper or lead comprises means for measuring the electrochemical potential present between the two faces of a solid electrolyte, one of these faces being in contact with the controlled oxygen pressure used as a reference, the other face being in contact with the metal under test, an outer tube having a high resistance to mechanical stresses, to thermal shocks, and to chemical attack, and is characterized in that the said tube surrounds the solid electrolyte, is fixed to the solid electrolyte, and forms a contact electrode with the liquid metal.
  • the solid electrolyte in that known apparatus may be shaped as a rod or strip, held in the end of an outer metal protective tube by means ofa cement.
  • This solid electrolyte is cemented into a refractory oxide ring D which has a high resistance to the passage of oxygen ions and may consist, for example, of alumina.
  • This refractory oxide ring is then cemented into the metal tube E, which in certain cases may be of mild steel or of alloy steel depending on the corrosive properties of the metal'into which the probe is to be immersed.
  • the lower ends of the tubes C and D are arranged above the lower and of the metal tube E along a distance ranging from I to about 5 cm depending on the conditions under which the probe is to be used;
  • the length and porosity of the cement column between the tube E and the refractory tube D are sufficient to allow the air to be slowly displaced in the volume at Z by the liquid metal which rises from the level Y to the level X under the influence of the hydrostatic pressure generated by the immersion.
  • the duration of i this displacement may advantageously vary between 10 few centimeters, for instance about 7 cm beyond the end ofthe electrolyte tube.
  • the lower end only of this tongue is dipped in the liquid metal and held in that position for a few minutes so that the heat is conducted from the bath to the refractory parts of the probe within the outer metal tube, with the result that these refractory parts are preheated prior to their immersion in the metal.
  • the preheating is improved when the outer tube is fitted at its lower and with an extension having the form of a sleeve which is designed to be dipped into the liquid metal before immersion of the cell in said liquid metal so that heat is conducted from the liquid metal to the cell in order to preheat the cell prior to immersion, and to contain a volume of trapped air which will be present between the surface of the liquid metal and the solid electrolyte when the cell is dipped in the liquid metal.
  • the preheating which is achieved by use of the sleeve, is more uniform and the temperature attained inside the probe is higher than can conveniently be obtained in practice by holding a probe without a sleeve just above the surface of the liquid metal.
  • the frequency of cracking of the solid electrolyte at the moment of immersion is strongly reduced by the use of such a sleeve.
  • A shows an oxygen reference electrode, which consists for example of gas or air or of a seconds and a few minutes, depending on the porosity and length of the cement column and on the volume of air trapped between X and Y.
  • the gas can have the possibility to escape through a small hole provided in the tube E at the level X, (not illustrated in the drawing).
  • the tubes of metal or alloy, used for E may advantageously be used as current conductors between the metal and the recording instrument.
  • the principal of the air gas trapped illustrated in the drawing may be advantageously applied when the tube E is not a metal or an alloy but any other refractory material such as silica, alumina or silicon carbide.
  • Apparatus for the continuous measurement of oxygen contained in a molten metal comprising a. a cell which comprises:
  • said outer tube containing at its lower end a projecting sleeve of high resistance to mechanical stresses, to thermal shocks and to chemical attacks;
  • said projecting sleeve being adapted to be dipped into the liquid metal before the cell is immersed in the liquid metal in order to conduct heat from the liquid metal to the cell and to preheat the cell prior to immersion;
  • said projecting sleeve being adapted to contain a volume of trapped air which is present between the surface of the liquid metal and the solid electrolyte when the cell is dipped into the liquid metal; and being adapted upon immersion to permit expansion of said trapped air to blow away slag, oxides, and other foreign particles which may be present on the surface of the metal being tested, and being adapted to reduce the thermal shock to which the solid electrolyte is subjected;
  • a column of cement provided between the outer tube and solid electrolyte wherein said cement is gas pervious for allowing said trapped air to be displaced by the hydrostatic pressure of the liquid metal upon immersion, and the porosity and length of the column of cement being adjusted to ensure delay between the immersion and rising of the liquid metal up to said solid electrolyte.
  • the apparatus of claim 1 which further comprises a refractory ring between said outer tube and said electrolyte wherein said refractory ring surrounds the side of said solid electrolyte and wherein said ring is joined to said solid electrolyte-and to said 'outer tube by a refractory cement.
  • Apparatus for the continuous measurement of oxygen contained in a molten metal comprising:
  • a cell which comprises i. means for measuring the electrochemical potential present between two faces of a solid oxygen electrolyte tube having a closed bottom;
  • said outer tube containing at its lower end a projecting sleeve of steel
  • a refractory ring surrounding the sides of said electrolyte tube; and being between said outer tube and said electrolyte tube;
  • said refractory ring being joined to said electrolyte tube and to said outer tube by refractory cement;
  • said projecting sleeve being adapted to be dipped into the liquid metal before the cell is immersed in the liquid metal in order to conduct heat from the liquid metal to the cell and to preheat the cell prior to immersion;
  • said projecting sleeve being adapted to contain a volume of air which is present between the surface of the liquid metal and the solid electrolyte tube when the cell is dipped into said liquid metal; and being adapted upon immersion to permit expansion of said trapped air to blow away slag, oxides, and other foreign particles which may be present on the surface of the metal being tested. and to reduce the thermal shock to which the solid electrolyte tube is subjected;
  • said refractory cement being gas pervious for allowing said trapped air to be displaced by the hydrostatic pressure of the liquid metal upon immersion, and for ensuring delay between the immersion and rising of the liquid metal up to said solid electrolyte.
  • cement between said outer tube and said solid electrolyte contains a metal oxide.

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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)
  • Investigating And Analyzing Materials By Characteristic Methods (AREA)
  • Measuring Oxygen Concentration In Cells (AREA)
US323493A 1972-01-31 1973-01-15 Apparatus for measuring in a continuous manner oxygen in a molten metal Expired - Lifetime US3864231A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
LU64699 1972-01-31

Publications (1)

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US3864231A true US3864231A (en) 1975-02-04

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US323493A Expired - Lifetime US3864231A (en) 1972-01-31 1973-01-15 Apparatus for measuring in a continuous manner oxygen in a molten metal

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US (1) US3864231A (ja)
JP (1) JPS5743866B2 (ja)
AU (1) AU467881B2 (ja)
GB (1) GB1360962A (ja)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4007106A (en) * 1973-06-22 1977-02-08 Canadian Patents And Development Limited Device for measuring oxygen concentration in molten-metal
US4166019A (en) * 1975-09-26 1979-08-28 General Electric Company Electrochemical oxygen meter
US4214967A (en) * 1977-11-08 1980-07-29 Westinghouse Electric Corp. Technique for reducing solid electrolyte cell drift
US5439579A (en) * 1991-11-26 1995-08-08 Tokyo Yogyo Kabushiki Kaisha Sensor probe for measuring hydrogen concentration in molten metal
US5989408A (en) * 1996-12-18 1999-11-23 Heraeus Electro-Nite International N.V. Process for measuring an electrochemical activity

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3864232A (en) * 1973-05-02 1975-02-04 Westinghouse Electric Corp Apparatus for Monitoring the Oxygen Content of High Temperature Fluids
CA990352A (en) * 1974-08-02 1976-06-01 Noranda Mines Limited Apparatus for the continuous measurement of the oxygen content of molten copper or alloys thereof
JPS5445107Y2 (ja) * 1975-03-03 1979-12-24
JPS5271295A (en) * 1975-12-11 1977-06-14 Furukawa Electric Co Ltd:The Cell for measuring oxygen quantity in molten metal
JPS5746155A (en) * 1980-09-05 1982-03-16 Nippon Kokan Kk <Nkk> Measuring sensor for oxygen concentration for molten metal
JPS59195560U (ja) * 1983-06-10 1984-12-26 山里エレクトロナイト株式会社 溶銑スラグ中の酸素量測定装置
JPH06105238B2 (ja) * 1986-02-06 1994-12-21 新日本製鐵株式会社 高炉内ガスの酸素分圧測定方法
WO2013131697A1 (de) * 2012-03-05 2013-09-12 Saint-Gobain Glass France Sonde zur kontinuierlichen messung der sauerstoffsättigung in metallschmelzen

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3481855A (en) * 1966-07-15 1969-12-02 United Nuclear Corp Continuous oxygen monitor for liquid metals
US3630874A (en) * 1967-11-17 1971-12-28 Siderurgie Fse Inst Rech Device for determining the activity of oxygen in molten metals
US3661749A (en) * 1968-02-09 1972-05-09 Metallurgie Hoboken Apparatus for measuring in a continuous manner the oxygen in a molten metal

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU524955B2 (en) * 1978-08-10 1982-10-14 Gentex Optics Inc Molding ophthalmic lenses and other articles

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3481855A (en) * 1966-07-15 1969-12-02 United Nuclear Corp Continuous oxygen monitor for liquid metals
US3630874A (en) * 1967-11-17 1971-12-28 Siderurgie Fse Inst Rech Device for determining the activity of oxygen in molten metals
US3661749A (en) * 1968-02-09 1972-05-09 Metallurgie Hoboken Apparatus for measuring in a continuous manner the oxygen in a molten metal

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4007106A (en) * 1973-06-22 1977-02-08 Canadian Patents And Development Limited Device for measuring oxygen concentration in molten-metal
US4166019A (en) * 1975-09-26 1979-08-28 General Electric Company Electrochemical oxygen meter
US4214967A (en) * 1977-11-08 1980-07-29 Westinghouse Electric Corp. Technique for reducing solid electrolyte cell drift
US5439579A (en) * 1991-11-26 1995-08-08 Tokyo Yogyo Kabushiki Kaisha Sensor probe for measuring hydrogen concentration in molten metal
US5989408A (en) * 1996-12-18 1999-11-23 Heraeus Electro-Nite International N.V. Process for measuring an electrochemical activity
US6156174A (en) * 1996-12-18 2000-12-05 Heraeus Electro-Nite International N.V. Immersion sensor for measuring an electrochemical activity

Also Published As

Publication number Publication date
AU467881B2 (en) 1975-12-18
JPS5743866B2 (ja) 1982-09-17
AU5159673A (en) 1974-08-01
GB1360962A (en) 1974-07-24
JPS4888994A (ja) 1973-11-21

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