US3758397A - Apparatus for oxygen determination - Google Patents
Apparatus for oxygen determination Download PDFInfo
- Publication number
- US3758397A US3758397A US00054986A US3758397DA US3758397A US 3758397 A US3758397 A US 3758397A US 00054986 A US00054986 A US 00054986A US 3758397D A US3758397D A US 3758397DA US 3758397 A US3758397 A US 3758397A
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- United States
- Prior art keywords
- tube
- rod
- body member
- electrolyte
- extends
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title abstract description 21
- 239000001301 oxygen Substances 0.000 title abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 title abstract description 21
- 239000003792 electrolyte Substances 0.000 abstract description 22
- 239000004020 conductor Substances 0.000 abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 14
- 239000000203 mixture Substances 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 13
- 239000012530 fluid Substances 0.000 abstract description 12
- 239000005350 fused silica glass Substances 0.000 abstract description 11
- 239000007784 solid electrolyte Substances 0.000 abstract description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 6
- 239000011733 molybdenum Substances 0.000 abstract description 6
- 239000007787 solid Substances 0.000 abstract description 5
- 229910000831 Steel Inorganic materials 0.000 description 21
- 239000010959 steel Substances 0.000 description 21
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 7
- 229910001338 liquidmetal Inorganic materials 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000000615 nonconductor Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 229910004160 TaO2 Inorganic materials 0.000 description 1
- 229910004369 ThO2 Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- G01N27/4112—Composition or fabrication of the solid electrolyte
-
- 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
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/06—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a liquid
-
- 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
- G01N27/416—Systems
- G01N27/417—Systems using cells, i.e. more than one cell and probes with solid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- Apparatus for measuring oxygen content of uids at elevated temperatures by means of a galvanic cell with a solid oxide electrolyte and a reference electrode of a mixture of a metal and its oxide includes a sensor which comprises a refractory body member having a rst longitudinal opening for receiving a fused silica tube which has the solid electrolyte fused to the end thereof which contacts the fluid.
- a rod of molybdenum or other conductor extends through the tube with the reference electrode between the end of the rod and the solid electrolyte.
- a second fused silica tube extends through a second longitudinal opening adjacent the first opening and contains a second rod of the same material as the tirst. The second rod also has its first end extending into the fluid.
- a thermocouple extends through the body member with its first end extending into the fluid and its second end connected to a connector.
- a steel lance has means at one end for receiving the connector and second ends of the rods and means at the other end for connecting to a voltage measuring means. In some instances the thermocouple maybe omitted.
- 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 determines 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 liquid copper and hot furnace gases.
- Apparatus suitable for this purpose is disclosed in the copending application of Fruehan and Turkdogan, Ser. No. 39,530, filed May 21, 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 view, mostly in longitudinal section of one embodiment of our invention
- FIG. 2 is a sectional view, similar to FIG. l, showing a second embodiment of our invention, but with the upper part of the apparatus and the connections to the potentiometer omitted;
- FIG. 3 is a view taken on line III- III of FIG. 2 with parts omitted;
- FIG. 4 is a viewtaken on line IV-IV of FIG. 2;
- FIG. 5 is a sectional view of the lower part of a third sensor of our invention.
- reference numeral 2 indicates the sensor unit of our apparatus.
- This includes a body member 4 which is made of a heat and thermal-shock resistant refractory such as cast aluminum oxide.
- a iirst longitudinal opening 6 extends through the body member 4 and contains a first tube 8 whose first end extends into the molten steel or other lluicl L.
- the tube 8 is made of an electrical insulator such as fused silica.
- a solid electrolyte in the form of a disc 10 of ZrO2 containing 3 to 10% by weight of CaO is fused to the inside of tube 8, and a reference electnode 12 in the form of a mixture of powdered Cr and Cr203 is placed on top of the electrolyte 10 in contact with the first end of a rod 14 which extends through tube 8 beyond the second end of body member 4.
- the rod 14 is made of an electrical conductor, preferably molybdenum.
- a second longitudinal opening 16 extends through the body member 4 adjacent to and generally parallel to opening 6.
- a tube 18, similar to tube 8, extends through opening 16 and receives a rod 20 of the same material as rod 14.
- the periphery of disc 10 is covered with a refractory coating 22 and the periphery of the first end of rod 20 is covered with a similar coating 24 to prevent too rapid disintegration of the disc and rod.
- the ends of the disc 10 and rod 20 are free of the coating which is preferably of the same composition as body member 4.
- a third longitudinal opening 26 is provided adjacent to and generally parallel to the openings 6 and 16, but does not extend the full length of the body member 4.
- the exposed upper ends of the thermocouple wires are coated with an epoxy or other impervious electrically insulating cement and are crimped into suitable thermocouple terminals 34.
- the second or top ends of rods 14 and 20 also act as terminals 14T and 20T.
- the sensor is preferably made as follows: The disc 10 is placed inside of tube 8 which is heated to a temperature at which it softens and flows around the disc 10. Upon cooling, the fused silica of tube 8 forms a tight seal around the disc 10 so as to prevent leakage of steel during immersion. If desired, a small diameter tube with a closed end made of the electrolyte material may be substituted for the tube 8 and disc 10. The mixture 12 is then tamped into the tube 8 and the rod 14 inserted into the tube in contact with the mixture 12. 'Ihe rod 20 is placed in tube 16 and the parts 28 to 34 assembled into one unit. All three tube assemblies are then placed in a mold cavity and held in essentially parallel relationship with each other and the axis of the mold cavity by means of a suitable fixture.
- a slurry of refractory particles and bonding agents mixed with Water is then poured into the cavity and around the stated components until the mold cavity is filled.
- Each of the component ends that must contact the molten steel project approximately 3A inch beyond one end of the mold and are not covered by the slurry.
- the other end of the components project beyond the opposite end of the mold and are not covered by the slurry.
- a small quantity of this slurry is painted onto the sides of the electrolyte disc 10 and the end of tube 8. However, the end surface of the electrolyte disc is not covered with slurry.
- the exposed length of rod 20 that contacts molten steel is covered with refractory slurry except for its end.
- the oxygen sensor unit is removed from the mold cavity and is subjected to a series of drying steps that will render the refractory body even stronger and free of moisture.
- lt is preferred to use a commercial refractory castable, such as Castola'st G, manufactured by the Harbison-Wa'lker Refractory Company, for this purpose and to follow their recommended for-ming and drying procedures.
- a steel lance 44 has a receptacle 46 at its lower end for receiving terminals 14T, 20T and 34, which are conneoted to a millivolt recorder 48, preferably a two-pen potentiometric Type-82 by means of a suitable twoconductor compensating lead wire 50 for the ther-mocouple and a two-conductor lead wire 52 for the oxygen cell.
- the length of lance 44 may be varied as desired and could also be omitted.
- Cardboard or ceramic sleeves 54 and 56 are preferably provided to protect the parts from overheating during immersion.
- the assembly In operation, the assembly is plunged into the melt to a suitable depth.
- the sleeves 54 and 56 which extend above the top of the melt, protect the Wires and upper elements of the sensor from damage by the metal.
- Caps 40 and 42 protect the sensor from chemical attack by the slag as it is lowered through the slag into the molten metal.
- CaO are in solid form and Fe-O is liquid).
- the following equation is obtained for weight percent oxygen in liquid steel in terms of ELMF (E) in rnillivolts and T in degrees Kelvin for the Cr-CR2O3 reference electrode and receives a rod 72 of While the specific components set forth above are preferred since -they have proven very sucessful in use in determining the oxygen content of liquid steel, they may be varied ,as long as they meet the following requirements.
- the electrolyte 10 must be a solid oxide and an oxygen ion conductor with insignificant electronic conductivity under the conditions of its use, particularly at the temperature and oxygen partial pressure to which it is subjected. It must not react with the materials it contacts.
- ZrOlg with 3 to 10% by weight of OaOf or MgO; ThO2 with 3 to 20% by weight of YgO, A1203 or MgO are examples of materials which are suitable under vlarying conditions, but all electrolytes are not all suitable for use with all types of fluids.
- the reference electrode 12 must be a condensed phase mixture of la metal and its oxide which does not readily melt at the temperature to which it is subjected no1 react significantly with the materials itv contacts.
- Cr-Cr2O'3 is most suitable for use with steel. MolMoOg, Ta-TaO2, W-Wo2, Ni-NiO, Fe-FeO, and (Eo-C00, may also be used, but not all can be used with all types of iiuids.
- the conductor rods 14 and 20 may be made of Pt, Rh, Pt and Rh, W, Ta, W and Re, Cr :and alloys thereof.
- Ni, Co, Fe, Cu, Al, Sn, Zn, Mg and their alloys may be used for testing most nonferrous metals including Al, Zn, Cu, Cr, Ni, Co and Sn and for testing most gases.
- it should be understood that it is the mechanical arrangement of the parts, nather than the specific materials used, that is the important feature of the invention.
- FIGS. 2, 3 and 4 show the preferred embodiment of our invention.
- This includes a body member 58 preferably made of the same material as body member 4 of the first embodiment.
- a rst longitudinal opening 60 extends through the body member and contains a first tube 62 whose rst end extends into the molten steel or other fluid L.
- the tube 62 is made of an electrical insulator such as fused quartz.
- a solid electrolyte in the form of a disc 63 of ZrOlz containing 3 to 101% by weight of CaO is fused to the inside of tube 62, and a reference electrode 64 in the form of a mixture of powdered Cr and Cr2O3 is placed on top of the electrolyte 63 and held in position by a retainer washer 65 which may be a refractory.
- a rod 66 in tube 62 has its first end bent and its second end extending through the tube 62 lbeyond the second end of body member 58.
- the rod 66 is made of ⁇ an electrical conductor, preferably molybdenum.
- the washer 65 has an opening 68 therethrough for receiving the bent end of rod 66 which extends longitudinal opening 70 ber 58 adjacent to and into the electrode 64.
- a second extends through the body memgenerally parallel to opening 60 the same material as rod 66.
- the exposed lower end of tube 62, the periphery of disc 68 and the exposed lower end of rod 72 may be covered with a refractory coating except for a short portion of the end of disc 63 and the end of rod 72.
- Third and fourth longitudinal openings 74 and 76 generally parallel to openings 60 and 70 receive a U-tube 78 made of fused quartz or other insulating material.
- Thermocouple wires 84 and 82 are received in the U-tube 78 and joined at the bend of the tube.
- This construction is essentially that shown in Mead Pat. No. 2,999,121.
- a body cap 84 of polyethylene or other electrically insulating material abuts the second end of body member 58 and also receives a polyethylene connector tube 86.
- Rod 66 passes through tube 86 with its top end bent around the bottom of a slot S8 in the tube 86 and back down the outside of the tube.
- Rod 72 likewise passes through tube 86 with its end bent around the free or top end of the tube.
- Thermocouple wire is connected to a conductor 90 which passes through tube 86 with its topend bent around the bottom of a slot 92 in the tube 86 to the outside of the tube.
- Thermocouple wire 82 is connected to a conductor 94 and passes through the tube 86 with its end bent around the bottom of a slot 96 in the tube 86 to the outside of the tube.
- the upper ends of Wires 80 and 82 are coated with an epoxy as in the first embodiment.
- a receptable 9S of insulating material such as rubber, having four spaced apart electrical contact rings 98a, 98b, 98e and 98d therein surrounds the tube 86 with the rings 98a, 98b, 98C, and 98d in contact with conductors 90, 94, 66 and 72, respectively.
- Four terminals 100:1, 100b, 100C and 100d secured in the end of receptacle 98 are electrically connected to rings 98a, 98b, 98e ⁇ and 98d, respectively.
- a receptacle adapter 102 made of steel or black iron pipe surrounds receptacle 98 and is connected by means of threaded insert 104 to a lance 106 corresponding to lance 44 of the first embodiment.
- a cardboard sleeve 108 surrounds the body member 58, body cap 84 and tubes 102 and 106.
- a steel protection cap 110 having a small hole 112 in the end thereof is secured to the sleeve 108.
- the connections of the terminals to the potentiometer may be as in the first embodiment and the operation is the same as that of the first embodiment. This embodiment is made in generally the same manner as the first embodiment.
- FIG. 5 shows a simplified and less expensive embodiment of our invention in which the thermocouple is omitted. Except for this omission the construction and materials are essentially the same as those of the other embodiments. This may be done because in many operations, particularly in steel making, other means are provided for continuously or intermittently measuring the temperature of the fluid and the temperature so obtained can be utilized in combination with the oxygen sensor to obtain an accurate oxygen reading.
- This embodiment includes a body member 114 made of the same material as body member 4.
- a first longitudinal opening 116 extends through the body member 114 and contains a silica tube 118 whose first end extends into the molten steel or other fiuid L.
- a solid electrolyte in the form of a disc 120 is fused to the inside of tube 118, and a reference electrode 122 in the form of a mixture of powdered Cr and Cr203 is placed on top of the electrolyte 120 in contact with the first end of a conductor rod 124 which extends through tube 118 beyond the second end of body member 114.
- a second longitudinal opening 126 extends through the body member 114 adjacent to and generally parallel to opening 116.
- a tube 128, similar to tube 118, may extend through opening 126 to receive a rod 130 of the same material as rod '124. If desired, the tube 118 may be omitted and the rod 130 received directly in opening 116.
- the remaining part of the sensor may be as shown in either of the other embodiments with the thermocouple connections omitted and hence are not shown or described here except to show a cardboard tube 132 and steel cap 134.
- apparatus for determining the oxygen content of a liquid metal which comprises a galvanie cell including said liquid metal as an electrode, a solid oxide electrolyte and a reference electrode, said electrolyte being an oxygen ion conductor having insignificant electronic conductivity under conditions of use, said reference electrode being a powdery mixture of a metal and its oxide, and means for measuring the EMF of the cell when the electrolyte contacts the liquid metal, the improvement comprising a sensor; said sensor including said electrolyte and said reference electrode, an elongated heat and thermal shock resistant body member of cast alumina adapted to be partially inserted into said liquid metal and having a plurality of longitudinal openings therein, a first fused silica tube extending through the first of said openings beyond both ends of said body member, a disc of said electrolyte fused to the inside of one end of said first tube spaced away from said body member and adapted to contact said liquid metal, means for containing said powdery mixture of a metal and its oxide Within said tube and in contact with said electro
- Apparatus according to claim 1 which includes a lance having means at one end for receiving said terminal means and means at its other end connected to said voltage measuring means, a cardboard sleeve surrounding at least a portion of said lance and said body member, and a steel cap surrounding the first end of said conductors and said thermocouple.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Pathology (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Immunology (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Measuring Oxygen Concentration In Cells (AREA)
- Polyesters Or Polycarbonates (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US5498670A | 1970-07-15 | 1970-07-15 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3758397A true US3758397A (en) | 1973-09-11 |
Family
ID=21994824
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00054986A Expired - Lifetime US3758397A (en) | 1970-07-15 | 1970-07-15 | Apparatus for oxygen determination |
Country Status (23)
Country | Link |
---|---|
US (1) | US3758397A (es) |
JP (1) | JPS5548256B1 (es) |
KR (1) | KR780000209B1 (es) |
AT (1) | AT316902B (es) |
BE (1) | BE769652A (es) |
BG (1) | BG20407A3 (es) |
CA (1) | CA936916A (es) |
CS (1) | CS166775B2 (es) |
DE (1) | DE2133631B2 (es) |
ES (1) | ES392920A1 (es) |
FI (1) | FI54744C (es) |
FR (1) | FR2100423A5 (es) |
GB (1) | GB1350663A (es) |
HU (1) | HU165461B (es) |
LU (1) | LU63525A1 (es) |
NL (1) | NL7109665A (es) |
NO (1) | NO133048C (es) |
PL (1) | PL70884B1 (es) |
RO (1) | RO56715A (es) |
SE (1) | SE379858B (es) |
TR (1) | TR16961A (es) |
YU (1) | YU175771A (es) |
ZA (1) | ZA714165B (es) |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3883408A (en) * | 1972-05-03 | 1975-05-13 | Inland Steel Co | Furnace atmosphere oxygen analysis apparatus |
US3935079A (en) * | 1972-11-03 | 1976-01-27 | Fitterer Engineering Associates, Inc. | Method and apparatus for displaying active oxygen and sensor temperature |
US4238957A (en) * | 1977-07-04 | 1980-12-16 | Commonwealth Scientific And Industrial Research Organization | Pyrometric sheath and process |
US4284487A (en) * | 1978-10-13 | 1981-08-18 | Milton Roy Company | Oxygen analyzer probe |
FR2485737A1 (fr) * | 1980-06-27 | 1981-12-31 | Siderurgie Fse Inst Rech | Dispositif de mesure de la teneur en oxygene d'atmosphere gazeuse |
US4342633A (en) * | 1978-04-06 | 1982-08-03 | Electro-Nite Co. | Oxygen sensor |
EP0059222A1 (en) * | 1980-09-05 | 1982-09-08 | Nippon Kokan Kabushiki Kaisha | Oxygen level sensor for molten metal |
US4378279A (en) * | 1981-08-31 | 1983-03-29 | Uop Inc. | High temperature electrical connection and method of producing same |
US4406754A (en) * | 1980-03-28 | 1983-09-27 | Kabushiki Kaisha Kobe Seiko Sho | Method and probe for the rapid determination of sulfur level |
EP0148492A1 (de) * | 1983-12-23 | 1985-07-17 | Thyssen Stahl Aktiengesellschaft | Vorrichtung zum Messen des Sauerstoffgehaltes und der Temperatur von Metallschmelzen während des Frischens in einem Konverter |
FR2601137A1 (fr) * | 1986-07-04 | 1988-01-08 | Centre Nat Rech Scient | Procede et dispositif pour la mesure des pressions partielles d'oxygene dans les gaz |
WO1988008131A1 (en) * | 1987-04-13 | 1988-10-20 | Allied Corporation | Method of assembly of an o2 assembly |
US5820739A (en) * | 1995-07-12 | 1998-10-13 | Robert Bosch Gmbh | Measuring instrument |
WO2004104534A1 (en) * | 2003-05-21 | 2004-12-02 | Rdc Contrôle Ltée | Composite ceramic device for measuring the temperature of liquids |
CN100458433C (zh) * | 2003-03-07 | 2009-02-04 | 贺利氏耐特电子国际有限公司 | 测定熔融金属或熔渣中氧活度的测量装置 |
CN104269197A (zh) * | 2014-09-27 | 2015-01-07 | 中国科学院合肥物质科学研究院 | 一种用于液态重金属反应堆堆内换料系统的验证装置 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
HU191839B (en) * | 1983-05-16 | 1987-04-28 | Nehezipari Mueszaki Egyetem | Method and device for measuring continuously the solute alumina content of cryolite melts with alumina content during operation |
FR2547656B1 (fr) * | 1983-06-14 | 1988-11-04 | Mannesmann Ag | Sonde de mesure de l'oxygene actif dans les masses metalliques en fusion |
FR2578981B1 (fr) * | 1985-03-13 | 1988-04-15 | Saint Gobain Vitrage | Sonde de mesure de la pression partielle en oxygene dans un bain de verre fondu |
DE3711497A1 (de) * | 1987-04-04 | 1987-10-15 | Eberhard Prof Dr Ing Steinmetz | Messzelle zur bestimmung des sauerstoffpotentials in gasen |
DE102013002389A1 (de) * | 2013-02-13 | 2014-08-14 | Minkon GmbH | Steckersystem, Messkopf, Kontaktstück, Verfahren zum Bestimmen einer Temperatur und einer elektromotorischen Kraft sowie Signalleitungsvorrichtung |
CN117849146A (zh) * | 2023-12-15 | 2024-04-09 | 钟祥市中原电子有限责任公司 | 一种铜液定氧电池及其制备工艺 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5438960U (es) * | 1977-08-24 | 1979-03-14 |
-
1970
- 1970-07-15 US US00054986A patent/US3758397A/en not_active Expired - Lifetime
-
1971
- 1971-06-23 CA CA116456A patent/CA936916A/en not_active Expired
- 1971-06-25 ZA ZA714165A patent/ZA714165B/xx unknown
- 1971-07-02 YU YU01757/71A patent/YU175771A/xx unknown
- 1971-07-05 ES ES392920A patent/ES392920A1/es not_active Expired
- 1971-07-06 DE DE2133631A patent/DE2133631B2/de not_active Withdrawn
- 1971-07-06 GB GB3172971A patent/GB1350663A/en not_active Expired
- 1971-07-07 BE BE769652A patent/BE769652A/xx unknown
- 1971-07-08 FR FR7125050A patent/FR2100423A5/fr not_active Expired
- 1971-07-12 RO RO67628A patent/RO56715A/ro unknown
- 1971-07-13 SE SE7109087A patent/SE379858B/xx unknown
- 1971-07-13 LU LU63525D patent/LU63525A1/xx unknown
- 1971-07-13 HU HUUE22A patent/HU165461B/hu unknown
- 1971-07-13 PL PL1971149426A patent/PL70884B1/pl unknown
- 1971-07-13 AT AT611271A patent/AT316902B/de not_active IP Right Cessation
- 1971-07-13 BG BG018057A patent/BG20407A3/xx unknown
- 1971-07-13 NL NL7109665A patent/NL7109665A/xx not_active Application Discontinuation
- 1971-07-13 TR TR16961A patent/TR16961A/xx unknown
- 1971-07-14 FI FI2000/71A patent/FI54744C/fi active
- 1971-07-14 NO NO2689/71A patent/NO133048C/no unknown
- 1971-07-14 KR KR7100977A patent/KR780000209B1/ko active
- 1971-07-15 CS CS5225A patent/CS166775B2/cs unknown
- 1971-07-15 JP JP5279671A patent/JPS5548256B1/ja active Pending
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3883408A (en) * | 1972-05-03 | 1975-05-13 | Inland Steel Co | Furnace atmosphere oxygen analysis apparatus |
US3935079A (en) * | 1972-11-03 | 1976-01-27 | Fitterer Engineering Associates, Inc. | Method and apparatus for displaying active oxygen and sensor temperature |
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 |
US4284487A (en) * | 1978-10-13 | 1981-08-18 | Milton Roy Company | Oxygen analyzer probe |
US4406754A (en) * | 1980-03-28 | 1983-09-27 | Kabushiki Kaisha Kobe Seiko Sho | Method and probe for the rapid determination of sulfur level |
FR2485737A1 (fr) * | 1980-06-27 | 1981-12-31 | Siderurgie Fse Inst Rech | Dispositif de mesure de la teneur en oxygene d'atmosphere gazeuse |
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. |
US4378279A (en) * | 1981-08-31 | 1983-03-29 | Uop Inc. | High temperature electrical connection and method of producing same |
EP0148492A1 (de) * | 1983-12-23 | 1985-07-17 | Thyssen Stahl Aktiengesellschaft | Vorrichtung zum Messen des Sauerstoffgehaltes und der Temperatur von Metallschmelzen während des Frischens in einem Konverter |
FR2601137A1 (fr) * | 1986-07-04 | 1988-01-08 | Centre Nat Rech Scient | Procede et dispositif pour la mesure des pressions partielles d'oxygene dans les gaz |
WO1988008131A1 (en) * | 1987-04-13 | 1988-10-20 | Allied Corporation | Method of assembly of an o2 assembly |
US5820739A (en) * | 1995-07-12 | 1998-10-13 | Robert Bosch Gmbh | Measuring instrument |
CN100458433C (zh) * | 2003-03-07 | 2009-02-04 | 贺利氏耐特电子国际有限公司 | 测定熔融金属或熔渣中氧活度的测量装置 |
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 |
CN104269197A (zh) * | 2014-09-27 | 2015-01-07 | 中国科学院合肥物质科学研究院 | 一种用于液态重金属反应堆堆内换料系统的验证装置 |
CN104269197B (zh) * | 2014-09-27 | 2016-08-24 | 中国科学院合肥物质科学研究院 | 一种用于液态重金属反应堆堆内换料系统的验证装置及其工作方法 |
Also Published As
Publication number | Publication date |
---|---|
KR780000209B1 (en) | 1978-05-26 |
ES392920A1 (es) | 1973-11-01 |
RO56715A (es) | 1974-09-01 |
SE379858B (es) | 1975-10-20 |
DE2133631A1 (de) | 1972-01-20 |
AT316902B (de) | 1974-08-12 |
ZA714165B (en) | 1972-03-29 |
GB1350663A (en) | 1974-04-18 |
NO133048C (es) | 1976-02-25 |
PL70884B1 (es) | 1974-04-30 |
CA936916A (en) | 1973-11-13 |
TR16961A (tr) | 1974-01-18 |
DE2133631B2 (de) | 1979-08-16 |
FR2100423A5 (es) | 1972-03-17 |
LU63525A1 (es) | 1971-11-16 |
BE769652A (fr) | 1972-01-07 |
FI54744C (fi) | 1979-02-12 |
NL7109665A (es) | 1972-01-18 |
NO133048B (es) | 1975-11-17 |
BG20407A3 (bg) | 1975-11-05 |
JPS5548256B1 (es) | 1980-12-04 |
FI54744B (fi) | 1978-10-31 |
HU165461B (es) | 1974-08-28 |
CS166775B2 (es) | 1976-03-29 |
YU175771A (en) | 1981-02-28 |
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