US3668099A - Apparatus for measuring oxygen content of a fluid - Google Patents

Apparatus for measuring oxygen content of a fluid Download PDF

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Publication number
US3668099A
US3668099A US115509A US3668099DA US3668099A US 3668099 A US3668099 A US 3668099A US 115509 A US115509 A US 115509A US 3668099D A US3668099D A US 3668099DA US 3668099 A US3668099 A US 3668099A
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United States
Prior art keywords
tube
flange
cap
button
sleeve
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Expired - Lifetime
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US115509A
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English (en)
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Robert S Rittiger
Charles K Russell
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United States Steel Corp
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United States Steel Corp
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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

Definitions

  • ABSTRACT Apparatus for measuring oxygen content of fluids at elevated temperatures includes a sensor or probe which comprises a Cr,0 tube and a solid electrolyte button sealing that end of the tube that contacts the fluid.
  • a solid oxygen reference material in the tube made of chromium or a chromium alloy contacts the button and the other end of the tube is sealed with a molybdenum cap.
  • a thermocouple and a lead wire pass through the cap into the tube.
  • a quartz tube surrounds the Cr,0, tube and button with its outer end in sealing engagement with the button.
  • An electronic conductor has one end extending into the fluid.
  • the conductor is a tube surrounding the quartz tube and in another it is a separate rod or tube.
  • the conductor is preferably a mixture of Al,0, and molybdenum.
  • the lead wire and the other end of the conductor are connected to a voltage measuring means.
  • This invention relates to apparatus for measuring the oxygen content and/or activity of fluids at elevated temperatures, and more particularly, to apparatus that rapidly deter mines the oxygen content of liquid steel in a furnace or container without removing a sample. Since our invention, at present, is most useful and most needed for this purpose, this use will be stressed hereinafter. However, our invention is also applicable for determining oxygen in other fluids at temperatures above approximately 700 C., such as oxygen in liquid copper or hot furnace gases. v
  • Apparatus suitable for this purpose is disclosed in the copending application of Fruehan and 'Turkdogan, Ser. No. 39,530, Filed May Ill, 1970.
  • the apparatus disclosed therein is basically laboratory apparatus and is not suitable for use in large steelmaking furnaces and containers because of cost, fragility, reliability when used by relatively unskilled workmen, ease of use and other factors important in adapting the basic cell concept to industrial use.
  • FIG. 1 is a sectional view of one embodiment of our invention.
  • FIG. 2 is an elevation, with parts broken away, and shown in section of another embodiment of our invention.
  • reference numeral 2 indicates a metallic oxide tube having its lower or outer end sealed by an electrolyte button 4 made of ZrO, containing 3 to 10% CaO and its upper or inner end sealed by a molybdenum cap 6. For best operation the size of the button is kept as small as possible.
  • An oxygen reference material8 is located within tube 2 in contact with button 4.
  • the reference material 8 must be liquid or solid at the operating temperature and is preferably chromium or a chromium alloy such as a Ni-Cr alloy. However, Mo, Ta, or an alloy thereof may be used.
  • the tube 2 must be an oxide of the reference metal, must not melt at the temperature of use, and must act as an electronic conductor at that temperature.
  • The-tube is preferably made of 0: 0,.
  • thermocouple 10 passes through cap 6 with its lower end extending into tube 2.
  • the thermocouple 10 may be of a standard straight type with its two wires passing through a 2- hole refractory insulator, but is preferably a standard U-tube type in which one wire is secured in each leg of the U-tube and connected at the center of the tube.
  • One such thermocouple is shown in Mead US. Pat. No. 2,999,121 dated Sept. 5, 1961, or 3,298,874 dated Jan. l7, 1967.
  • a refractory insulated molybdenum wire 12 passes throughcap 6 into tube 2 and is held in place by set screw 14.
  • a quartz tube 16 surrounds tube 2 with its lower end in sealing engagement with button 4 which does not extend beyond the end of the tube 16.
  • the tube 16 includes an outwardly extending radial flange 16F at its upper end.
  • a slight clearance such as l mm. should be provided between tubes 2 and 16 to prevent cracking of tube 16 due to thermal expansion.
  • a cermet tube 18 closely surrounds the tube 16 and has its bottom tapered inwardly with an opening therein for exposure of the button 4 to the fluid F being analyzed.
  • the tube 18 has an outwardly extending radial flange 18F at its upper end which abuts flange 16F.
  • the tube 18 must be made of a material which is an electronic conductor and will not melt at the temperature of use. its metallic phase should be the same as that of cap 6 and wire 12 since otherwise a thermoelectric correction must be made to the electrolytic cell reading.
  • An internally threaded sleeve 20 surrounds flanges 16F and 18F and has a bottom flange 20F which bears against flange 18F.
  • a cap 22 has a threaded reduced diameter section 24 which is threaded into sleeve 20 to hold the parts assembled.
  • the cap 22 has a hole 26 therethrough for passage of the insulated thermocouple wires and wire 12.
  • a wire 28, preferably made of molybdenum, is attached to cap 22 by means of a screw 30.
  • the sleeve 20 and cap 22 must be electrically conductive and are preferably fabricated from the same metal as the metal phase of the cermet tube 18, but if these parts are at a reasonably uniform temperature in use, no significant thenno-electric error is created if the parts are made of stainless steel.
  • the thermocouple wires and wires 12 and 28 are connected to a potentiometer 32. If the assembled unit is to be placed in a metal bath F with a portion of the cermet tube 18 exposed to slag or to air, a refractory oxide sleeve 34 of a material resistant to slag attack and oxidation is preferably placed over that portion of tube 18 so exposed.
  • Sleeves made of aluminum oxide or magnesium oxide are examples of such protective refractory materials, but this does not exclude other refractory oxides or combinations thereof.
  • a metal cap 36 is placed over the end of the sensor to protect the electrolyte. This cap must be made of a material which will melt upon contacting the molten metal.
  • a steel protective cap is usually employed.
  • the quartz tube 16 may be heated so that it flows around the electrolyte button 4.
  • Another method is to precision grind the electrolyte button 4 so that it just fits inside the quartz tube 16. ln either case, the end of the tube 16 should not extend beyond the electrolyte button and should be ground off, if necessary.
  • the senor can either be partially immersed (about one half of its length) from above the metal bath or installed in the side wall or bottom of a refractory container such as a steel ladle.
  • the molten metal F containing an unknown amount of dissolved oxygen content contacts the exposed end of the zirconia button 4 and also the exposed end of cermet tube 18 which is an electrical conductor.
  • an electrical connection is made from button 4 through tube 18, sleeve 20, cap 22 and lead 28 to potentiometer 32.
  • An electrical connection is also made from button 4, through the reference alloy 8, oxide tube 2, cap 6 and wire 12 to the other terminal of potentiometer 32.
  • the enif that is read, in combination with the temperature, can be mathematically converted to oxygen content by the general formulas shown in the Fruehan et al. application.
  • a separate rod 40 is used in place of tube 18 and is made of the same material as that tube.
  • One end of the rod 40 is inserted in the fluid F and the other end connected by means of lead 42 to potentiometer 32.
  • Those parts of probe 44 within quartz tube 16' are the same as in the first embodiment of the invention and are indicated by the same reference numerals.
  • Tube 16 differs from tube 16 by the omission of flange 16F.
  • a protective alumina tube 46 surrounds the tube 16' and is cemented thereto by refractory cement.
  • the tube 46 has a radial flange 46F at its inner end.
  • a protective metal cap 36' may be provided over the lower end of tube 16' for the same reason as cap 36 in H6. 1.
  • This embodiment is less expensive than the first embodiment because the cost of the rod 40 is substantially less than the cost of tube 18. The operation of this embodiment is essentially the same as that of the first embodiment.
  • Apparatus for measuring the oxygen content of a fluid comprising a first tube, an electrolyte button sealing the outer end of said first tube and adapted to contact said fluid, a metallic oxygen reference material within said first tube in contact with said button, said reference material being nonvolatile at the operating temperature, said first tube being an oxide of the metal of said oxygen reference material and acting as an electronicconductor at the operating temperature, a thermocouple passing into said first tube and having leads connected to its inner-end, a lead wire electrically connected to said first tube, a second tube surrounding said first tube and said button with its outer end in sealing engagement with said button, said leads and lead wire passing through said second tube, a second electronic conductor adapted to contact said fluid, and means connected to said lead wire and said second electronic conductor to measure the voltage flow through said fluid.
  • said first tube is made of (3,0,
  • said button is made of ZrO, containing 3 to l% CaO
  • said reference material is of the class consisting of chromium and chromium alloys
  • said electronic conductor is a mixture of Al,0 and molybdenum.
  • Apparatus according to claim 3 including a molybdenum cap sealing the upper end of said first tube with said lead wire and thermocouple passing therethrough.
  • Apparatus according to claim 4 including a flange extending radially outward from the inner end of said second tube, a flange extending radially outward from the inner end of said third tube and abutting the flange on said second tube, an internally threaded sleeve surrounding said flanges and having a flange engaging the flange on said third tube, a male threaded cap threaded into said sleeve, and a lead extending between said cap and said voltage measuring means.
  • Apparatus according to claim 6 including a protective sleeve surrounding a portion of said third tube with one end bearing against the flange of said stainless steel sleeve.
  • Apparatus according to claim 8 including a protective sleeve surrounding said third tube on the inner sideof said first tube.
  • Apparatus according to claim 8 including a flange extending radially outward from the inner end of said second tube, a flange extending radially outward from the inner end of said third tube and abutting the flange on said second tube, an internally threaded sleeve surrounding said flanges and having a flange engaging the flange on said third tube, a male threaded cap threaded into said sleeve, and a lead extending between said cap and said voltage measuring means.
  • Apparatus according to claim 1 including a cap sealing the upper end-of said first tube with said lead wire and thermocouple passing therethrough.
US115509A 1971-02-16 1971-02-16 Apparatus for measuring oxygen content of a fluid Expired - Lifetime US3668099A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US11550971A 1971-02-16 1971-02-16

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US (1) US3668099A (xx)
AT (1) AT340707B (xx)
AU (1) AU460260B2 (xx)
BE (1) BE779350A (xx)
BR (1) BR7200803D0 (xx)
CA (1) CA934443A (xx)
CS (1) CS179965B2 (xx)
DE (1) DE2206589C3 (xx)
ES (1) ES399842A1 (xx)
FR (1) FR2125906A5 (xx)
GB (1) GB1381976A (xx)
IT (1) IT949110B (xx)
LU (1) LU64786A1 (xx)
NL (1) NL7201858A (xx)
SE (1) SE378677B (xx)
SU (1) SU506333A3 (xx)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2305864A1 (fr) * 1975-03-27 1976-10-22 Leeds & Northrup Co Pile galvanique
DE2808621A1 (de) * 1977-03-01 1978-09-07 Toyota Motor Co Ltd Sauerstoffmessfuehler und verfahren zu dessen herstellung
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
DE2900069A1 (de) * 1979-01-02 1980-07-03 Ferrotron Elektronik Gmbh Messkopf zur ermittlung der sauerstoffaktivitaet von schmelzen
US4238957A (en) * 1977-07-04 1980-12-16 Commonwealth Scientific And Industrial Research Organization Pyrometric sheath and process
FR2485737A1 (fr) * 1980-06-27 1981-12-31 Siderurgie Fse Inst Rech Dispositif de mesure de la teneur en oxygene d'atmosphere gazeuse
FR2578981A1 (fr) * 1985-03-13 1986-09-19 Saint Gobain Vitrage Sonde de mesure de la pression partielle en oxygene dans un bain de verre fondu
FR2589579A1 (fr) * 1983-05-16 1987-05-07 Nehezipari Mueszaki Egyetem Dispositif pour mesurer la teneur en oxyde d'aluminium d'un bain de cryolite se trouvant dans un four d'electrolyse d'aluminium
US6328867B1 (en) * 2000-05-04 2001-12-11 Ethem Tugrul Turkdogan Sensors for measuring the solute contents of liquid ferrous and non-ferrous metals
WO2004104534A1 (en) * 2003-05-21 2004-12-02 Rdc Contrôle Ltée Composite ceramic device for measuring the temperature of liquids

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL178627C (nl) * 1973-02-19 1986-04-16 Estel Hoogovens Bv Meetcel voor het bepalen van het gehalte aan vrije zuurstof in een bad gesmolten metaal.
DE2833397C2 (de) * 1978-07-29 1985-06-20 Ferrotron Elektronik Gmbh Meßzelle
DE2934244C2 (de) * 1979-08-24 1984-10-31 Ferrotron Elektronik Gmbh Meßzelle
DE2954228C2 (xx) * 1979-08-24 1989-06-22 Fischer, Wilhelm Anton, Prof. Dr.-Ing.Habil.
CH684852A5 (de) * 1991-06-07 1995-01-13 Mettler Toledo Ag Temperaturfühler für potentiometrische Messketten und Verfahren zu seiner Herstellung.
GB9206367D0 (en) * 1992-03-24 1992-05-06 Pilkington Plc Oxygen measuring probe
DE4438523C1 (de) * 1994-10-31 1995-12-07 Schott Geraete Multifunktions-Sensor

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1094180A (en) * 1965-10-14 1967-12-06 Hoesch Ag Improvements in or relating to metallic analysis
GB1191222A (en) * 1967-09-15 1970-05-13 Canadian Patents Dev Apparatus for the Direct Determination of a Gas in a Molten Metal

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1094180A (en) * 1965-10-14 1967-12-06 Hoesch Ag Improvements in or relating to metallic analysis
GB1191222A (en) * 1967-09-15 1970-05-13 Canadian Patents Dev Apparatus for the Direct Determination of a Gas in a Molten Metal

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
G. R. Fitterer, J. Metals, 18, 961 (1966). *
G. R. Fitterer, J. Metals, 19, 92, (1967). *
G. R. Fitterer, J. Metals, 20, 27, (1967). *
Thomas C. Wilder, Trans. of the Metallurgical Society of Aime, Vol. 236, pp. 1035 1040, July 1966. *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2305864A1 (fr) * 1975-03-27 1976-10-22 Leeds & Northrup Co Pile galvanique
DE2808621A1 (de) * 1977-03-01 1978-09-07 Toyota Motor Co Ltd Sauerstoffmessfuehler und verfahren zu dessen herstellung
US4238957A (en) * 1977-07-04 1980-12-16 Commonwealth Scientific And Industrial Research Organization Pyrometric sheath and process
US4342633A (en) * 1978-04-06 1982-08-03 Electro-Nite Co. Oxygen sensor
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
DE2900069A1 (de) * 1979-01-02 1980-07-03 Ferrotron Elektronik Gmbh Messkopf zur ermittlung der sauerstoffaktivitaet von schmelzen
FR2485737A1 (fr) * 1980-06-27 1981-12-31 Siderurgie Fse Inst Rech Dispositif de mesure de la teneur en oxygene d'atmosphere gazeuse
FR2589579A1 (fr) * 1983-05-16 1987-05-07 Nehezipari Mueszaki Egyetem Dispositif pour mesurer la teneur en oxyde d'aluminium d'un bain de cryolite se trouvant dans un four d'electrolyse d'aluminium
FR2578981A1 (fr) * 1985-03-13 1986-09-19 Saint Gobain Vitrage Sonde de mesure de la pression partielle en oxygene dans un bain de verre fondu
US6328867B1 (en) * 2000-05-04 2001-12-11 Ethem Tugrul Turkdogan Sensors for measuring the solute contents of liquid ferrous and non-ferrous metals
WO2004104534A1 (en) * 2003-05-21 2004-12-02 Rdc Contrôle Ltée Composite ceramic device for measuring the temperature of liquids
US20070160427A1 (en) * 2003-05-21 2007-07-12 Claude Allaire Composite ceramic device for measuring the temperature of liquids
US7882620B2 (en) 2003-05-21 2011-02-08 Groupe Refraco Inc. Composite ceramic device for measuring the temperature of liquids

Also Published As

Publication number Publication date
BE779350A (fr) 1972-08-14
GB1381976A (en) 1975-01-29
NL7201858A (xx) 1972-08-18
ES399842A1 (es) 1975-04-01
IT949110B (it) 1973-06-11
SE378677B (xx) 1975-09-08
FR2125906A5 (xx) 1972-09-29
AU3886372A (en) 1973-08-16
DE2206589A1 (de) 1972-08-17
CS179965B2 (en) 1977-12-30
AU460260B2 (en) 1975-04-24
BR7200803D0 (pt) 1973-05-17
AT340707B (de) 1977-12-27
LU64786A1 (xx) 1972-07-04
DE2206589C3 (de) 1982-01-21
CA934443A (en) 1973-09-25
SU506333A3 (ru) 1976-03-05
DE2206589B2 (de) 1981-04-16
ATA123172A (de) 1977-04-15

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