US3787308A - Oxygen sensor - Google Patents

Oxygen sensor Download PDF

Info

Publication number
US3787308A
US3787308A US00226937A US3787308DA US3787308A US 3787308 A US3787308 A US 3787308A US 00226937 A US00226937 A US 00226937A US 3787308D A US3787308D A US 3787308DA US 3787308 A US3787308 A US 3787308A
Authority
US
United States
Prior art keywords
gas
oxygen
cell
cathode
flow
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.)
Expired - Lifetime
Application number
US00226937A
Inventor
F Malaspina
W Aker
J Werth
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ESB Inc
Original Assignee
ESB Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by ESB Inc filed Critical ESB Inc
Application granted granted Critical
Publication of US3787308A publication Critical patent/US3787308A/en
Assigned to CONGRESS FINANCIAL CORPORATION; A CORP OF CA. reassignment CONGRESS FINANCIAL CORPORATION; A CORP OF CA. SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). AGAINST PATENTS AND APPLICATIONS NOT CROSSED OFF Assignors: EXIDE CORPORATION
Assigned to NATIONAL BANK OF CANADA, A BANKING CORP. OF CANADA reassignment NATIONAL BANK OF CANADA, A BANKING CORP. OF CANADA SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). (AGAINST PATS. AND APPLS. NOT CROSSED OFF) Assignors: EXIDE CORPORATION
Assigned to EXIDE CORPORATION reassignment EXIDE CORPORATION SECURITY AGREEMENT RECORDED MARCH 31, 1983, REEL 4122-FRAMES 001 TO 074 IS HEREBY TERMINATED Assignors: CONGRESS FINANCIAL CORPORATION
Assigned to CHEMICAL BANK, A NY BANKING CORPORATION reassignment CHEMICAL BANK, A NY BANKING CORPORATION SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DIXIE BATTERY COMPANY, ESB PUERTO RICO CORP., EXIDE CORPORATION, GENERAL BATTERY CORPORATION
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403Cells and electrode assemblies
    • G01N27/404Cells with anode, cathode and cell electrolyte on the same side of a permeable membrane which separates them from the sample fluid, e.g. Clark-type oxygen sensors

Definitions

  • a comparator element for gaseous oxygen comprises a first and a second oxygen-inert metal electrochemical cell.
  • the first cell is fed with an oxygen containing gas of known oxygen content and the second cell is fed with a gas of unknown oxygen content.
  • the design of the electrochemical cells is such that their electrical resistance when current is passed therethrough is inversely proportional to the oxygen content of the feed v gas over a useful range.
  • an accurate determination of the oxygen content of the unknown gas may be made with self compensation for ambient temperature.
  • the range of the instrument may be increased by restricting the flow of gas to the oxygen electrodes. This may be accomplished by flowing the gas through a diffusion membrane and an orifice.
  • Oxygen evolved from the metal electrode of the standard cell may be used to feed the oxygen electrode of the same cell thus providing a self sustaining standard atmosphere.
  • the comparator may be compensated for pressure by providing pressure equalizing means between the gas feed to the first cell and the gas feed to the second.
  • This invention relates to gas monitoring and analysis devices. In particular it relates to devices for monitoring or analyzing the oxygen in a gas.
  • Oxygen deficiency indicating devices are required when men must work in confined spaces such as mines, vats, tanks, etc. Oxygen determination apparatus is also a requisite in such diverse application as space ships and capsules, submarines for military and civilian use as well as combustion control and other environmental studies.
  • Oxygen determination apparatus is also a requisite in such diverse application as space ships and capsules, submarines for military and civilian use as well as combustion control and other environmental studies.
  • the gas chromatograph is useful for analyzing the composition of even very minute gas samples.
  • the chromatograph is a large and delicate instrument suitable for laboratory work but not adapted to everyday use in industry. Small chemical absorption tubes have been perfected to measure oxygen, but these are of limited usefulness.
  • a comparator element for gaseous oxygen comprises a first and a second oxygen-inert metal electrochemical cell.
  • the first cell is fed gas containing oxygen of known concentration and the second cell is fed gas containing an unknown concentration of oxygen.
  • the polarizatio'n resistance provides a measure of the comparative concentration of oxygen in the feeds.
  • the range of the device is extended by constricting the flow of gas to the cells.
  • Oxygen evolved at the anode of the companion cell may be used to feed the cathode thereof thus providing a self sustained reference. Compensation for ambient pressure may be provided by introducing pressure equalizing means between the two cells.
  • the cells may be made quite small, of the order of 1 sq. cm.
  • a simple electriclal bridge circuit fed from a single dry cell is sufficient for most applications. This can be arranged to provide low or high level oxygen alarms or may be used to directly read the percentage of oxygen present.
  • the device of the invention can be made small in size, low in cost,
  • FIG. 1 depicts in cross section a simplified sensorreference cell of the invention
  • FIG. 2 depicts the reference cell of FIG. 1 connected in a bridge circuit for an oxygen sensor or alarm;
  • FIG. 3 depicts a performance curve of the sensor relating current flow through the cell with the content of oxygen fed to it;
  • FIG. 4 depicts a second embodiment of the sensorreference cell of the invention
  • FIG. 5 depicts a second form of electrical circuit for use with the sensor-reference cell of the invention
  • FIG. 6 depicts the sensor of the invention connected for measuring gases from a chimney stack.
  • 10 represents in cross section a cylindrical housing enclosing two electrochemical cell means.
  • the housing might be made from insulated metal or from one of the common structural plastics such as methacrylate, styrene, etc. It must be non-reactive with the strongly alkaline electrolyte. If a cemented construction is used, it should be a cementable material, and it should be dimensionally stable.
  • An electrical lead 20 is attached to each electrode 12.
  • Two identical oxygen electrodes 22 and 24 form the end walls of the compartments 16 and 18.
  • Electrical leads 26 and 28 are attached to electrode 22 and 24.
  • the electrodes can be any of the known oxygen consuming electrode structures.
  • An oxygen consuming electrode that has been found particularly suitable can be made as follows: carbon powder and Teflon (polytetrafluoroethylene) in the ratio of about four to one by weight are mixed and formed into a porous sheet on rolls. The sheet so formed is pressed onto an expanded nickel sheet or other grid structure. A sheet of microporous non-wetting material such as Teflon (polytetrafluoroethylene) is then adhered by head and pressure to one side of the above structure to form a triple laminate. In this electrode of the microporous sheet side faces the gas to provide microporosity to the electrode and to provide an hydrophobic surface to prevent leakage of electrolyte therethrough.
  • the carbon particles provide catalytic sites and the screen serves as a current collector
  • the two cell compartments 16 and 18 are filled with a suitable alkaline electrolyte such as potassium hydroxide solution. Covered vents 30 and 32 provide access to the two compartments.
  • a suitable alkaline electrolyte such as potassium hydroxide solution.
  • FIG. 2 shows a typical bridge circuit using the sensor of FIG. 1.
  • 16 and 18 represent the two cell compartments and the two cell means.
  • Resistors 44 and 46 connect the two air electrodes 22 and 24 to the negative of battery 48.
  • Battery 48 need be only a single cell as 1.3 volts has been found to be ample for driving the circuit.
  • one or both resistors 44 and 46 may be adjustable. The adjustable feature is useful in calibrating the instrument.
  • a signalling device such as the meter 50 is connected to the electrical leads of the gas electrodes.
  • Other signaling devices include means such as a light or bell. Alternately an activator for a value or damper may be caused to operate from the bridge circuit.
  • FIG. 3 shows a typical current oxygen curve for such a cell. Above about percent oxygen the cell becomes saturated with oxygen and the proportionality relationship no longer holds.
  • the cell can be likened to a variable resistor whose resistance value within the operating range is inversely proportioned to the oxygen content.
  • one of the cells is exposed to an oxygen source of a known concentration and the other cell, 24 is exposed to a source of unknown or varying oxygen content.
  • concentration of oxygen of the unknown is equal to that of the known source, the bridge will be balanced; otherwise it will be out of balance.
  • the device described will only be useful for measuring or comparing oxygen concentration below about 5 percent. Above this, the cell becomes insensitive as shown in curve FIG. 3.
  • a constriction can be put in the line feeding the known and unknown gasses to the cell.
  • various forms of orifice could be used, it has been found preferably to use a combination of an orifice and a diffusion membrane.
  • the diffusion membrane should be a true diffusion membrane rather than a porous screen.
  • Thin sections (5 to mils thick) of such materials as natural and silicone rubber, polytetrafluoroethylene, fluorinated ethylene-propylene co-polymer, polybutadiene, poly(butadiene-styrene) ethyl cellulose, cellulose acetate and protein enriched triacetate cellulose make excellent membranes. Excellent results have been found when the membrane is chosen from such materials as silicone rubber, or protein enriched triacetate cellulose in thin sections.
  • the range of the oxygen sensing cells can be extended to cover the entire range of zero to 100 percent oxygen.
  • FIG. 4 shows a cell design having diffusion membranes 60 and orifices 62 located in the passage feeding the gas electrodes 22 and 24. This cell also uses a single anode 13 for simplicity.
  • a further refinement of the reference cell is shown in dotted lines in FIG. 4. It has been noted that oxygen is produced from the electrode 13. The amount of oxygen given off in each cell must be axactly equal to the oxygen consumed by the oxygen electrodes.
  • a conduit 64 is shown carrying oxygen from the cell compartment 16 to a chamber 66 feeding orifice 62, difiusion membrane and gas electrode 22. With this construction the oxygen concentration in the cell defined by compartment l6 and electrode 22 will remain constant and at the value which was present when the cell is put in operation. Thus the cell means with the oxygen return conduit becomes an excellent reference cell. It is self contained and can be operated in any environment without affecting its output.
  • Another feature of the sensor is that by providing a means for equalizing the pressure between compartments 66 and 64, the sensor becomes self compensating for pressure.
  • a simple pressure equalizing means is to have a flexible gas bag attached to the feed-back tube 64. Where cell 24 is fed from a closed system, an enclosed bellows device may be used. Because both cells are closely associated and can be made conveniently small, the sensor has an automatic compensation for temperature.
  • the electrical circuit of FIG. 2 is very convenient when the sensor is used for an oxygen level control or alarm.
  • the bridge balance point is adjusted by means of a variable resistance 46 so that the null point of the bridge is at the oxygen level which it is desired to monitor.
  • the polarity of the electric potential at meter 50 will be in one direction.
  • the level crosses into the danger area the potential will reverse.
  • Means for converting the reverse signal into a control or alarm signal are well known; for example a reverse voltage relay or an operational amplifier could be placed at 50 to give a power signal capable of operating a valve or energizing a light bulb or horn.
  • the sensor cell may be used as a direct reading oxygen meter.
  • a possible circuit for this purpose is shown in FIG. 5.
  • This circuit is similar to the circuit of FIG. 2 except that a meter 70 calibrated in percent oxygen having a paralleled variable resistance shunt 72 and a variable resistor 74 make up the resistor of the bridge indicated by 46 of FIG. 2.
  • a convenient reference gas is air of 21 percent oxygen.
  • the bridge is then balanced by combined adjustment of resistors 72 and 74. When balanced, meter 50 will be at its null point and meter 70 will point to the percent oxygen in the standard gas.
  • cell 18 is fed the unknown gas and cell 16 is fed with the standard gas. The percent oxygen will be proportional to the current flow through the cell 18.
  • the oxygen sensor of this invention is capable of being built in a small size and in fact by making it small the lag time required to reach equilibrium will be made small; the electrical circuiting can likewise be made small. It is self contained and can be energized by a single dry cell. It is also rugged and truly portable. Thus it differs considerably from the classical oxygen sensing and measuring devices such as the orsat, the thermal cell and the gas chromatograph. These features make it particularly adaptable as a personal oxygen detector for miners, resuce workers and people working in enclosed spaces. Because of its builtin pressure compensation, it is suitable for deep diving work where a small simple direct reading device is of extreme importance. For the same reason it is suitable for aerospace applications where pressures are below atmospheric.
  • the electrolyte of the cell of the invention is a reactive to a gas such as carbon dioxide.
  • a gas such as carbon dioxide.
  • gasses may be present as in a flue gas it is necessary to pass the gas through a carbon dioxide absorption column prior to feeding it to the sensor cell.
  • FIG. 6 shows chimney 80 connected by tube 8 2 to carbon dioxide absorption tube 84.
  • Tube 86 feeds the washed gas to the sensor side 88 of gas analyzer means 90.
  • a continuous flow of flue gas through the system is provided by a gas pump as for instance the aspirator 92.
  • the standard side 94 of the analyzer 90 receives a continuous supply of oxygen from its gassing electrode via the feed back tube 96.
  • a pressure equalizer 100 comprising a sealed vessel 102 with an internal flexible wall 104 is provided to equalize the gas pressures between cell means 88 and 94 by means of tubes 106 and 108 respectively.
  • a comparator for comparing the oxygen concentration of a gas of unknown oxygen content with the oxygen concentration of a gas of known oxygen content which comprises:
  • a first electrochemical resistance cell comprising a first oxygen consuming cathode receiving a first gas of known oxygen concentration, a first electrolyte and an inert metallic gassing anode;
  • a second electrochemical resistance cell comprising a second oxygen consuming cathode receiving a second gas of unknown oxygen concentration, a second electrolyte and an inert metallic gassing anode;
  • a housing containing the first electrochemical cell and the second electrochemical cell; means for supplying a positive current to the cathode of the first electrochemical cell to produce a first resistive drop across the first electrochemical cell the first drop being dependent upon the oxygen concentration of the first gas;
  • a comparator as defined in claim ll including a first and a second means for restricting gas How, the first means for restricting gas flow restricting the flow of gas to the cathode of the first electrochemical cell and the second means for restricting gas flow restricting the flow of gas to the cathode and the second electrochemical cell.
  • a comparator as defined in claim 3 wherein the material from which the first and the second diffusion membranes are made is selected from the group which consists of natural rubber, silicone rubber, polytetrafluoroethylene, fluorinated ethylene-propylene copolymer, polybutadiene, poly(butadiene-styrene), ethyl cellulose, cellulose acetate, and protein enriched triacetate cellulose.
  • a comparator as defined in claim 1 including conduit means for conducting oxygen gas given off by the anode of the first electrochemical cell to the cathode thereof.
  • a comparator as defined in claim 6 including means equalizing the pressure within the first electrochemical resistance cell to the pressure within the second electrochemical resistance cell.
  • each oxygen gas consuming cathode comprises a laminate of metallic grid, a porous sheet of carbon and polytetrafluoroethylene, and a sheet of microporous polytetrafluoroethylene, the side of the laminate bearing the grid being exposed to the electrolyte of the cell and the side of the laminate bearing the microporous sheet being exposable to an oxygen containing gas.
  • a comparator as defined in claim 1 wherein the means for comparing the resistance defined by the second drop with the resistance defined by the first drop comprises a four armed electrical bridge circuit.
  • An oxygen meter for determining the oxygen concentration of a gas of unknown oxygen content which comprises:
  • first electrochemical resistance cell comprising a first oxygen consuming cathode receiving a first gas of known oxygen concentration, a first electrolyte and an inert metallic gassing anode;
  • a second electrochemical resistance cell comprising a second oxygen consuming cathode receiving a second gas of unknown oxygen concentration, a second electrolyte and an inert metallic gassing an ode;
  • f. means for supplying an equal and predetermined positive potential to the cathode of the first electrochemical cell and to the cathode of the second l reshwisa ss V.
  • An oxygen meter as defined in claim 1 1 including a first and a second means for restricting gas flow, the first means for restricting gas flow restricting the flow of gas to the cathode of the first electrochemical cell and the second means for restricting gas flow restricting the flow of gas to the cathode of the second electrochemical cell.
  • An oxygen meter as defined in claim 13 wherein the material from which the first and the second diffusion membranes are made is selected from the group which consists of natural rubber, silicone rubber, polytetrafluoroethylene, fluorinated ethylene-propylene co-polymer, polybutadiene, poly(butadiene-styrene),
  • ethyl cellulose cellulose acetate
  • protein enriched triacetate cellulose ethyl cellulose, cellulose acetate, and protein enriched triacetate cellulose.
  • An oxygen meter as defined in claim 1 1 including conduit means for conducting oxygen gas given off by the anode of the first electrochemical cell to the cathode thereof.
  • An oxygen meter as defined in claim 16 including means equalizing the pressure within the first electrochemical resistance cell to the pressure within the second electrochemical resistance cell.
  • each oxygen gas consuming cathode comprises a laminate of a metallic grid, a porous sheet of carbon and polytetrafluoroethylene, and a sheet of microporous polytetrafluoroethylene, the side of the laminate bearing the grid being exposed to the electrolyte of the cell and the side of the laminate bearing the microporous sheet being exposable to an oxygen containing gas.

Abstract

A comparator element for gaseous oxygen comprises a first and a second oxygen-inert metal electrochemical cell. The first cell is fed with an oxygen containing gas of known oxygen content and the second cell is fed with a gas of unknown oxygen content. The design of the electrochemical cells is such that their electrical resistance when current is passed therethrough is inversely proportional to the oxygen content of the feed gas over a useful range. By comparing the resistances of the two cells, an accurate determination of the oxygen content of the unknown gas may be made with self compensation for ambient temperature. The range of the instrument may be increased by restricting the flow of gas to the oxygen electrodes. This may be accomplished by flowing the gas through a diffusion membrane and an orifice. Oxygen evolved from the metal electrode of the standard cell may be used to feed the oxygen electrode of the same cell thus providing a self sustaining standard atmosphere. The comparator may be compensated for pressure by providing pressure equalizing means between the gas feed to the first cell and the gas feed to the second.

Description

ited States Patent [191 alaspina et al.
[ Jan. 22, 1974 OXYGEN SENSOR [75] Inventors: Francis P. Malaspina, Yardley;
Wesley E. Aker, Malvem, both of Pa.; John Werth, Princeton, NJ.
[52] US. Cl. 204/195 P, 204/1 T, 204/195 R,
204/195 M [51] Int. Cl.. G011! 27/26, GOlh 27/28, GOln 27/46 [58] Field of Search. 204/195 R, l T, 195 M, 195 P Primary ExaminerG. L. Kaplan [57] ABSTRACT A comparator element for gaseous oxygen comprises a first and a second oxygen-inert metal electrochemical cell. The first cell is fed with an oxygen containing gas of known oxygen content and the second cell is fed with a gas of unknown oxygen content. The design of the electrochemical cells is such that their electrical resistance when current is passed therethrough is inversely proportional to the oxygen content of the feed v gas over a useful range. By comparing the resistances of the two cells, an accurate determination of the oxygen content of the unknown gas may be made with self compensation for ambient temperature. The range of the instrument may be increased by restricting the flow of gas to the oxygen electrodes. This may be accomplished by flowing the gas through a diffusion membrane and an orifice. Oxygen evolved from the metal electrode of the standard cell may be used to feed the oxygen electrode of the same cell thus providing a self sustaining standard atmosphere. The comparator may be compensated for pressure by providing pressure equalizing means between the gas feed to the first cell and the gas feed to the second.
20 Claims, 6 Drawing Figures OXYGEN SENSOR BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to gas monitoring and analysis devices. In particular it relates to devices for monitoring or analyzing the oxygen in a gas.
2. Description of the Prior Art The science of determining the oxygen concentration in a gas has undergone a considerable evolution. One of the first oxygen deficiency sensors was the mine canary. A more scientific classical method is by chemical absorption such as is performed in an Orsat gas analyzer. This is slow and not easily adapted to continuous reading. Devices for measuring the thermal conductivity of gas have been perfected. These provide continuous readings but require a considerable volume of gas for proper functioning.
Oxygen deficiency indicating devices are required when men must work in confined spaces such as mines, vats, tanks, etc. Oxygen determination apparatus is also a requisite in such diverse application as space ships and capsules, submarines for military and civilian use as well as combustion control and other environmental studies. In spite of the many devices available, there is still a need for a small reliable oxygen sensor and analyzer operable by unskilled people and capable of reading a wide range of oxygen concentration. The gas chromatograph is useful for analyzing the composition of even very minute gas samples. However, the chromatograph is a large and delicate instrument suitable for laboratory work but not adapted to everyday use in industry. Small chemical absorption tubes have been perfected to measure oxygen, but these are of limited usefulness. Most recently fuel cell art has been utilized to provide a device which measures the oxygen content of a gas by the output of an oxygen-fuel electrochemical cell. Such cells can be made small in size, so that they may be carried about by a worker without inconvenience. However, they are subjected to loss of calibration due to the inconsistencies of the fuel cell.
SUMMARY OF THE INVENTION A comparator element for gaseous oxygen comprises a first and a second oxygen-inert metal electrochemical cell. The first cell is fed gas containing oxygen of known concentration and the second cell is fed gas containing an unknown concentration of oxygen. When current is passed through the cells, the polarizatio'n resistance provides a measure of the comparative concentration of oxygen in the feeds. The range of the device is extended by constricting the flow of gas to the cells. Oxygen evolved at the anode of the companion cell may be used to feed the cathode thereof thus providing a self sustained reference. Compensation for ambient pressure may be provided by introducing pressure equalizing means between the two cells. The cells may be made quite small, of the order of 1 sq. cm. electrode area and requiring a feed in the order of 1/10 cc gas per second. A simple electriclal bridge circuit fed from a single dry cell is sufficient for most applications. This can be arranged to provide low or high level oxygen alarms or may be used to directly read the percentage of oxygen present.
It will be seen from this description that the device of the invention can be made small in size, low in cost,
rugged and portable. It is ideally suited to wear by workers such as miners, divers astronauts, etc. The self compensation provided by the use of two cells removes all problems usually associated with temperature, age, etc., while the use of a gassing cathode rather than a fuel cathode as used in certain presently available devices removes the uncertainty associated with the fuel electrode such as loss of catalytic power, poisoning, as well as the need to carry a fuel supply.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 depicts in cross section a simplified sensorreference cell of the invention;
FIG. 2 depicts the reference cell of FIG. 1 connected in a bridge circuit for an oxygen sensor or alarm;
FIG. 3 depicts a performance curve of the sensor relating current flow through the cell with the content of oxygen fed to it;
FIG. 4 depicts a second embodiment of the sensorreference cell of the invention;
FIG. 5 depicts a second form of electrical circuit for use with the sensor-reference cell of the invention; and FIG. 6 depicts the sensor of the invention connected for measuring gases from a chimney stack.
DESCRIPTION OF THE PREFERRED O ENTS,
In FIG. 1, 10 represents in cross section a cylindrical housing enclosing two electrochemical cell means. The housing might be made from insulated metal or from one of the common structural plastics such as methacrylate, styrene, etc. It must be non-reactive with the strongly alkaline electrolyte. If a cemented construction is used, it should be a cementable material, and it should be dimensionally stable. There are four electrodes located in the housing, two to each cell means. The first two of these, 12, are gassing electrodes made from an impervious sheet of inert metal such as nickel. They are held tightly in housing 10 by ring 14 and are also sealed in position by a cement compatible with the material of the housing10. The two electrodes separate the two cell compartments l6 and 18. An electrical lead 20 is attached to each electrode 12. Two identical oxygen electrodes 22 and 24 form the end walls of the compartments 16 and 18. Electrical leads 26 and 28 are attached to electrode 22 and 24. The electrodes can be any of the known oxygen consuming electrode structures. An oxygen consuming electrode that has been found particularly suitable can be made as follows: carbon powder and Teflon (polytetrafluoroethylene) in the ratio of about four to one by weight are mixed and formed into a porous sheet on rolls. The sheet so formed is pressed onto an expanded nickel sheet or other grid structure. A sheet of microporous non-wetting material such as Teflon (polytetrafluoroethylene) is then adhered by head and pressure to one side of the above structure to form a triple laminate. In this electrode of the microporous sheet side faces the gas to provide microporosity to the electrode and to provide an hydrophobic surface to prevent leakage of electrolyte therethrough. The carbon particles provide catalytic sites and the screen serves as a current collector.
The two cell compartments 16 and 18 are filled with a suitable alkaline electrolyte such as potassium hydroxide solution. Covered vents 30 and 32 provide access to the two compartments.
FIG. 2 shows a typical bridge circuit using the sensor of FIG. 1. 16 and 18 represent the two cell compartments and the two cell means. Resistors 44 and 46 connect the two air electrodes 22 and 24 to the negative of battery 48. Battery 48 need be only a single cell as 1.3 volts has been found to be ample for driving the circuit. For convenience, one or both resistors 44 and 46 may be adjustable. The adjustable feature is useful in calibrating the instrument. To complete the bridge circuit a signalling device such as the meter 50 is connected to the electrical leads of the gas electrodes. Other signaling devices include means such as a light or bell. Alternately an activator for a value or damper may be caused to operate from the bridge circuit.
It is to be noted that when a direct current power source of fixed voltage is connected to cell means such as shown in FIG. 2 with the positive of the source connected to the nickel electrode and the negative of the source connected to the gas electrode, the current flow through the cell will be directly proportional to the oxygen available at the gas electrode. FIG. 3 shows a typical current oxygen curve for such a cell. Above about percent oxygen the cell becomes saturated with oxygen and the proportionality relationship no longer holds. The cell can be likened to a variable resistor whose resistance value within the operating range is inversely proportioned to the oxygen content.
To use the sensor in the bridge circuit of FIG. 2, one of the cells, say, 22, is exposed to an oxygen source of a known concentration and the other cell, 24 is exposed to a source of unknown or varying oxygen content. When the concentration of oxygen of the unknown is equal to that of the known source, the bridge will be balanced; otherwise it will be out of balance. The device described will only be useful for measuring or comparing oxygen concentration below about 5 percent. Above this, the cell becomes insensitive as shown in curve FIG. 3. As a means to overcome this limitation, a constriction can be put in the line feeding the known and unknown gasses to the cell. Although various forms of orifice could be used, it has been found preferably to use a combination of an orifice and a diffusion membrane. The diffusion membrane should be a true diffusion membrane rather than a porous screen. Thin sections (5 to mils thick) of such materials as natural and silicone rubber, polytetrafluoroethylene, fluorinated ethylene-propylene co-polymer, polybutadiene, poly(butadiene-styrene) ethyl cellulose, cellulose acetate and protein enriched triacetate cellulose make excellent membranes. Excellent results have been found when the membrane is chosen from such materials as silicone rubber, or protein enriched triacetate cellulose in thin sections. By the use of the orifice and diffusion membrane, the range of the oxygen sensing cells can be extended to cover the entire range of zero to 100 percent oxygen. FIG. 4 shows a cell design having diffusion membranes 60 and orifices 62 located in the passage feeding the gas electrodes 22 and 24. This cell also uses a single anode 13 for simplicity.
A further refinement of the reference cell is shown in dotted lines in FIG. 4. It has been noted that oxygen is produced from the electrode 13. The amount of oxygen given off in each cell must be axactly equal to the oxygen consumed by the oxygen electrodes. A conduit 64 is shown carrying oxygen from the cell compartment 16 to a chamber 66 feeding orifice 62, difiusion membrane and gas electrode 22. With this construction the oxygen concentration in the cell defined by compartment l6 and electrode 22 will remain constant and at the value which was present when the cell is put in operation. Thus the cell means with the oxygen return conduit becomes an excellent reference cell. It is self contained and can be operated in any environment without affecting its output.
Another feature of the sensor is that by providing a means for equalizing the pressure between compartments 66 and 64, the sensor becomes self compensating for pressure. When the sensor is to be used in the open, i.e., with the complete device immersed in the gas of unknown oxygen content, a simple pressure equalizing means is to have a flexible gas bag attached to the feed-back tube 64. Where cell 24 is fed from a closed system, an enclosed bellows device may be used. Because both cells are closely associated and can be made conveniently small, the sensor has an automatic compensation for temperature.
The electrical circuit of FIG. 2 is very convenient when the sensor is used for an oxygen level control or alarm. For such use, the bridge balance point is adjusted by means of a variable resistance 46 so that the null point of the bridge is at the oxygen level which it is desired to monitor. As long as the oxygen level stays on the safe side of the null point, the polarity of the electric potential at meter 50 will be in one direction. However, if the level crosses into the danger area, the potential will reverse. Means for converting the reverse signal into a control or alarm signal are well known; for example a reverse voltage relay or an operational amplifier could be placed at 50 to give a power signal capable of operating a valve or energizing a light bulb or horn.
Because of th linearity of the cell potential with respect to oxygen content of the sensed gas, the sensor cell may be used as a direct reading oxygen meter. A possible circuit for this purpose is shown in FIG. 5. This circuit is similar to the circuit of FIG. 2 except that a meter 70 calibrated in percent oxygen having a paralleled variable resistance shunt 72 and a variable resistor 74 make up the resistor of the bridge indicated by 46 of FIG. 2. To operate the oxygen meter, the two sides of the sensor are fed from the same gas supply of known oxygen content. A convenient reference gas is air of 21 percent oxygen. The bridge is then balanced by combined adjustment of resistors 72 and 74. When balanced, meter 50 will be at its null point and meter 70 will point to the percent oxygen in the standard gas. To measure a gas of unknown oxygen content, cell 18 is fed the unknown gas and cell 16 is fed with the standard gas. The percent oxygen will be proportional to the current flow through the cell 18.
It will be observed that the oxygen sensor of this invention is capable of being built in a small size and in fact by making it small the lag time required to reach equilibrium will be made small; the electrical circuiting can likewise be made small. It is self contained and can be energized by a single dry cell. It is also rugged and truly portable. Thus it differs considerably from the classical oxygen sensing and measuring devices such as the orsat, the thermal cell and the gas chromatograph. These features make it particularly adaptable as a personal oxygen detector for miners, resuce workers and people working in enclosed spaces. Because of its builtin pressure compensation, it is suitable for deep diving work where a small simple direct reading device is of extreme importance. For the same reason it is suitable for aerospace applications where pressures are below atmospheric. The device is useful in the process and other industries where control or measurement of oxy gen content is required. Unfortunately, the electrolyte of the cell of the invention is a reactive to a gas such as carbon dioxide. Thus where such gasses may be present as in a flue gas it is necessary to pass the gas through a carbon dioxide absorption column prior to feeding it to the sensor cell.
When an unknown gas is fed to the sensor via a tube, it is necessary that the atmosphere to which the sensor is exposed is not materially changed by the oxygen consumed by the sensor. To achieve this, it is desirable to have a flow of gas across the sensor area. As an example, FIG. 6 shows chimney 80 connected by tube 8 2 to carbon dioxide absorption tube 84. Tube 86 feeds the washed gas to the sensor side 88 of gas analyzer means 90. A continuous flow of flue gas through the system is provided by a gas pump as for instance the aspirator 92. The standard side 94 of the analyzer 90 receives a continuous supply of oxygen from its gassing electrode via the feed back tube 96. A pressure equalizer 100 comprising a sealed vessel 102 with an internal flexible wall 104 is provided to equalize the gas pressures between cell means 88 and 94 by means of tubes 106 and 108 respectively.
Other uses of the device of the invention will be obvious to those skilled in the art of gas sensing and analy- SIS.
Having fully described our invention and given examples of its embodiment as well as pointing out numerous sites where it will be of use, we claim:
1. A comparator for comparing the oxygen concentration of a gas of unknown oxygen content with the oxygen concentration of a gas of known oxygen content which comprises:
a. a first electrochemical resistance cell comprising a first oxygen consuming cathode receiving a first gas of known oxygen concentration, a first electrolyte and an inert metallic gassing anode;
b. a second electrochemical resistance cell comprising a second oxygen consuming cathode receiving a second gas of unknown oxygen concentration, a second electrolyte and an inert metallic gassing anode;
c. a housing containing the first electrochemical cell and the second electrochemical cell; means for supplying a positive current to the cathode of the first electrochemical cell to produce a first resistive drop across the first electrochemical cell the first drop being dependent upon the oxygen concentration of the first gas;
e. means for supplying a positive current to the cathode of the second electrochemical cell to produce a second resistive drop across the second electrochemical cell the second drop being dependent upon the oxygen concentration of the second gas;
2. A comparator as defined in claim ll including a first and a second means for restricting gas How, the first means for restricting gas flow restricting the flow of gas to the cathode of the first electrochemical cell and the second means for restricting gas flow restricting the flow of gas to the cathode and the second electrochemical cell.
3. A comparator as defined in claim 2 wherein the first means for restricting the flow of gas to the first cathode includes a first diffusion membrane and the second means for restricting the flow of gas to the second cathode includes a second diffusion membrane.
4. A comparator as defined in claim 3 wherein the material from which the first and the second diffusion membranes are made is selected from the group which consists of natural rubber, silicone rubber, polytetrafluoroethylene, fluorinated ethylene-propylene copolymer, polybutadiene, poly(butadiene-styrene), ethyl cellulose, cellulose acetate, and protein enriched triacetate cellulose.
5. A comparator as defined in claim 2 wherein the first means for restricting the flow of gas to the first cathode includes a first orifice and the second means for restricting the flow of gas to the second cathode includes a second orifice.
6. A comparator as defined in claim 1 including conduit means for conducting oxygen gas given off by the anode of the first electrochemical cell to the cathode thereof.
7. A comparator as defined in claim 6 including means equalizing the pressure within the first electrochemical resistance cell to the pressure within the second electrochemical resistance cell.
8. A comparator as defined in claim 1 wherein each oxygen gas consuming cathode comprises a laminate of metallic grid, a porous sheet of carbon and polytetrafluoroethylene, and a sheet of microporous polytetrafluoroethylene, the side of the laminate bearing the grid being exposed to the electrolyte of the cell and the side of the laminate bearing the microporous sheet being exposable to an oxygen containing gas.
9. A comparator as defined in claim 1 wherein the means for comparing the resistance defined by the second drop with the resistance defined by the first drop comprises a four armed electrical bridge circuit.
10. A comparator element as defined in claim 1 wherein the inert metallic anode of the first electrochemical cell is a first side of a metallic anode and the inert metallic anode of the second electrochemical cell in the second side of said metallic anode.
11. An oxygen meter for determining the oxygen concentration of a gas of unknown oxygen content which comprises:
a. first electrochemical resistance cell comprising a first oxygen consuming cathode receiving a first gas of known oxygen concentration, a first electrolyte and an inert metallic gassing anode;
b. a second electrochemical resistance cell comprising a second oxygen consuming cathode receiving a second gas of unknown oxygen concentration, a second electrolyte and an inert metallic gassing an ode;
c. a housing containing the first electrochemical cell and the second electrochemical cell;
' d. means for supplying a positive current to the cathode of the first electrochemical cell to produce a first resistive drop across the first electrochemical cell the first drop being dependent upon the oxygen concentration of the first gas;
e. means for supplying a positive current to the cathode of the second electrochemical cell to produce a second resistive drop across the second electrochemical cell the second drop being dependent upon the oxygen concentration of the second gas;
f. means for supplying an equal and predetermined positive potential to the cathode of the first electrochemical cell and to the cathode of the second l reshwisa ss V.
g. means for measuring the flow of current to the 9sth9 9 the $99M sq qshsm 521 9 7 h. calibration means for directly relating the magnitude of the flow of current to the oxygen concentration of the gas of unknown oxygen content.
12. An oxygen meter as defined in claim 1 1 including a first and a second means for restricting gas flow, the first means for restricting gas flow restricting the flow of gas to the cathode of the first electrochemical cell and the second means for restricting gas flow restricting the flow of gas to the cathode of the second electrochemical cell.
13. An oxygen meter as defined in claim 12 wherein the first means for restricting the flow of gas to the first cathode includes a first diffusion membrane and the second means for restricting the flow of gas to the second cathode includes a second diffusion membrane.
14. An oxygen meter as defined in claim 13 wherein the material from which the first and the second diffusion membranes are made is selected from the group which consists of natural rubber, silicone rubber, polytetrafluoroethylene, fluorinated ethylene-propylene co-polymer, polybutadiene, poly(butadiene-styrene),
ethyl cellulose, cellulose acetate, and protein enriched triacetate cellulose.
15. An oxygen meter as defined in claim 12 wherein the first means for restricting the flow of gas to the first cathode includes a first orifice and the second means for restricting the flow of gas to the second cathode includes a second orifice.
16. An oxygen meter as defined in claim 1 1 including conduit means for conducting oxygen gas given off by the anode of the first electrochemical cell to the cathode thereof.
17. An oxygen meter as defined in claim 16 including means equalizing the pressure within the first electrochemical resistance cell to the pressure within the second electrochemical resistance cell.
18. An oxygen meter as defined in claim 11 wherein each oxygen gas consuming cathode comprises a laminate of a metallic grid, a porous sheet of carbon and polytetrafluoroethylene, and a sheet of microporous polytetrafluoroethylene, the side of the laminate bearing the grid being exposed to the electrolyte of the cell and the side of the laminate bearing the microporous sheet being exposable to an oxygen containing gas.
19. An oxygen meter as defined in claim 11 wherein the means for supplying a positive potential includes an electrochemical battery, and the means for measuring the current flow including a four armed electrical bridge circuit.
20. An oxygen meter as defined in claim 11 wherein the inert metallic anode of the first electrochemical cell is a first side of a metallic anode and the inert metallic anode of the second electrochemical cell is the second side of said metallic anode.

Claims (19)

  1. 2. A comparator as defined in claim 1 including a first and a second means for restricting gas flow, the first means for restricting gas flow restricting the flow of gas to the cathode of the first electrochemical cell and the second means for restricting gas flow restricting the flow of gas to the cathode and the second electrochemical cell.
  2. 3. A comparator as defined in claim 2 wherein the first means for restricting the flow of gas to the first cathode includes a first diffusion membrane and the second means for restricting the flow of gas to the second cathode includes a second diffusion membrane.
  3. 4. A comparator as defined in claim 3 wherein the material from which the first and the second diffusion membranes are made is selected from the group which consists of natural rubber, silicone rubber, polytetrafluoroethylene, fluorinated ethylene-propylene co-polymer, polybutadiene, poly(butadiene-styrene), ethyl cellulose, cellulose acetate, and protein enriched triacetate cellulose.
  4. 5. A comparator as defined in claim 2 wherein the first means for restricting the flow of gas to the first cathode includes a first orifice and the second means for restricting the flow of gas to the second cathode includes a second orifice.
  5. 6. A comparator as defined in claim 1 including conduit means foR conducting oxygen gas given off by the anode of the first electrochemical cell to the cathode thereof.
  6. 7. A comparator as defined in claim 6 including means equalizing the pressure within the first electrochemical resistance cell to the pressure within the second electrochemical resistance cell.
  7. 8. A comparator as defined in claim 1 wherein each oxygen gas consuming cathode comprises a laminate of metallic grid, a porous sheet of carbon and polytetrafluoroethylene, and a sheet of microporous polytetrafluoroethylene, the side of the laminate bearing the grid being exposed to the electrolyte of the cell and the side of the laminate bearing the microporous sheet being exposable to an oxygen containing gas.
  8. 9. A comparator as defined in claim 1 wherein the means for comparing the resistance defined by the second drop with the resistance defined by the first drop comprises a four armed electrical bridge circuit.
  9. 10. A comparator element as defined in claim 1 wherein the inert metallic anode of the first electrochemical cell is a first side of a metallic anode and the inert metallic anode of the second electrochemical cell in the second side of said metallic anode.
  10. 11. An oxygen meter for determining the oxygen concentration of a gas of unknown oxygen content which comprises: a. first electrochemical resistance cell comprising a first oxygen consuming cathode receiving a first gas of known oxygen concentration, a first electrolyte and an inert metallic gassing anode; b. a second electrochemical resistance cell comprising a second oxygen consuming cathode receiving a second gas of unknown oxygen concentration, a second electrolyte and an inert metallic gassing anode; c. a housing containing the first electrochemical cell and the second electrochemical cell; d. means for supplying a positive current to the cathode of the first electrochemical cell to produce a first resistive drop across the first electrochemical cell the first drop being dependent upon the oxygen concentration of the first gas; e. means for supplying a positive current to the cathode of the second electrochemical cell to produce a second resistive drop across the second electrochemical cell the second drop being dependent upon the oxygen concentration of the second gas; f. means for supplying an equal and predetermined positive potential to the cathode of the first electrochemical cell and to the cathode of the second electrochemical cell; g. means for measuring the flow of current to the cathode of the second electrochemical cell; and h. calibration means for directly relating the magnitude of the flow of current to the oxygen concentration of the gas of unknown oxygen content.
  11. 12. An oxygen meter as defined in claim 11 including a first and a second means for restricting gas flow, the first means for restricting gas flow restricting the flow of gas to the cathode of the first electrochemical cell and the second means for restricting gas flow restricting the flow of gas to the cathode of the second electrochemical cell.
  12. 13. An oxygen meter as defined in claim 12 wherein the first means for restricting the flow of gas to the first cathode includes a first diffusion membrane and the second means for restricting the flow of gas to the second cathode includes a second diffusion membrane.
  13. 14. An oxygen meter as defined in claim 13 wherein the material from which the first and the second diffusion membranes are made is selected from the group which consists of natural rubber, silicone rubber, polytetrafluoroethylene, fluorinated ethylene-propylene co-polymer, polybutadiene, poly(butadiene-styrene), ethyl cellulose, cellulose acetate, and protein enriched triacetate cellulose.
  14. 15. An oxygen meter as defined in claim 12 wherein the first means for restricting the flow of gas to the first cathode includes a first orifice and the second means for restricting the flow of gas to the second cathode includes a seCond orifice.
  15. 16. An oxygen meter as defined in claim 11 including conduit means for conducting oxygen gas given off by the anode of the first electrochemical cell to the cathode thereof.
  16. 17. An oxygen meter as defined in claim 16 including means equalizing the pressure within the first electrochemical resistance cell to the pressure within the second electrochemical resistance cell.
  17. 18. An oxygen meter as defined in claim 11 wherein each oxygen gas consuming cathode comprises a laminate of a metallic grid, a porous sheet of carbon and polytetrafluoroethylene, and a sheet of microporous polytetrafluoroethylene, the side of the laminate bearing the grid being exposed to the electrolyte of the cell and the side of the laminate bearing the microporous sheet being exposable to an oxygen containing gas.
  18. 19. An oxygen meter as defined in claim 11 wherein the means for supplying a positive potential includes an electrochemical battery, and the means for measuring the current flow including a four armed electrical bridge circuit.
  19. 20. An oxygen meter as defined in claim 11 wherein the inert metallic anode of the first electrochemical cell is a first side of a metallic anode and the inert metallic anode of the second electrochemical cell is the second side of said metallic anode.
US00226937A 1972-02-16 1972-02-16 Oxygen sensor Expired - Lifetime US3787308A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US22693772A 1972-02-16 1972-02-16

Publications (1)

Publication Number Publication Date
US3787308A true US3787308A (en) 1974-01-22

Family

ID=22851084

Family Applications (1)

Application Number Title Priority Date Filing Date
US00226937A Expired - Lifetime US3787308A (en) 1972-02-16 1972-02-16 Oxygen sensor

Country Status (1)

Country Link
US (1) US3787308A (en)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3886058A (en) * 1973-07-30 1975-05-27 Texas Instruments Inc Gas sensing electrode system employing hydrophilic wick
US4071429A (en) * 1976-12-29 1978-01-31 Monsanto Company Electrolytic flow-cell apparatus and process for effecting sequential electrochemical reaction
DE2752530A1 (en) * 1976-11-24 1978-06-01 Westinghouse Electric Corp ANALYZER FOR COMBUSTIBLE COMPONENTS IN A FUEL GAS ATMOSPHERE
US4132616A (en) * 1976-03-11 1979-01-02 City Technology Limited Gas sensor
US4267023A (en) * 1977-10-17 1981-05-12 Orion Research Incorporated Chemically integrating dosimeter and gas analysis methods
US4324257A (en) * 1978-02-20 1982-04-13 U.S. Philips Corporation Device for the transcutaneous measurement of the partial oxygen pressure in blood
US4324632A (en) * 1979-05-17 1982-04-13 City Technology Limited Gas sensor
US4334510A (en) * 1978-11-21 1982-06-15 Thomson-Csf Electrochemical sensor for measuring relative concentrations of reactive species in a fluid mixture and a system comprising said sensor, especially for regulation
EP0078627A1 (en) * 1981-10-19 1983-05-11 Westinghouse Electric Corporation Improved solid electrolyte gas sensing apparatus
US4563249A (en) * 1983-05-10 1986-01-07 Orbisphere Corporation Wilmington, Succursale De Collonge-Bellerive Electroanalytical method and sensor for hydrogen determination
US4808293A (en) * 1986-12-19 1989-02-28 Matsushita Electric Industrial Co., Ltd. Oxygen sensor and method of making such sensor
US5092980A (en) * 1990-02-23 1992-03-03 Dragerwerk Aktiengesellschaft Measuring apparatus for detecting gases
US5178744A (en) * 1988-10-31 1993-01-12 Fujikura Ltd. Oxygen sensor device
EP0756172A1 (en) * 1995-07-26 1997-01-29 Praxair Technology, Inc. Neural network compensation for sensors
US5668302A (en) * 1995-05-24 1997-09-16 City Technology Limited Electrochemical gas sensor assembly
US5906718A (en) * 1995-04-21 1999-05-25 Mine Safety Appliances Company Electrochemical gas sensor for the detection of nitrogen dioxide
US6404205B1 (en) * 1997-05-09 2002-06-11 Japan Storage Battery Co., Ltd. Method for testing the reliability of an electrochemical gas sensor
US20100136444A1 (en) * 2005-09-21 2010-06-03 Nash David A Electrical bridge for fuel cell plates
WO2017060380A1 (en) * 2015-10-09 2017-04-13 Flexenable Limited Sensing device and method of producing the same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3149921A (en) * 1961-07-20 1964-09-22 Gen Electric Method of measuring the partial pressure of a gas
US3296113A (en) * 1963-10-15 1967-01-03 Union Carbide Corp Gas-stream monitor
US3328204A (en) * 1963-04-08 1967-06-27 Gen Electric Process of electrical energy generation utilizing alkanes and phosphoric acid
US3594233A (en) * 1968-07-19 1971-07-20 Yardney International Corp Rechargeable gas-polarized cell
US3647641A (en) * 1970-10-26 1972-03-07 Gen Electric Reactant sensor and method of using same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3149921A (en) * 1961-07-20 1964-09-22 Gen Electric Method of measuring the partial pressure of a gas
US3328204A (en) * 1963-04-08 1967-06-27 Gen Electric Process of electrical energy generation utilizing alkanes and phosphoric acid
US3296113A (en) * 1963-10-15 1967-01-03 Union Carbide Corp Gas-stream monitor
US3594233A (en) * 1968-07-19 1971-07-20 Yardney International Corp Rechargeable gas-polarized cell
US3647641A (en) * 1970-10-26 1972-03-07 Gen Electric Reactant sensor and method of using same

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3886058A (en) * 1973-07-30 1975-05-27 Texas Instruments Inc Gas sensing electrode system employing hydrophilic wick
US4132616A (en) * 1976-03-11 1979-01-02 City Technology Limited Gas sensor
DE2752530A1 (en) * 1976-11-24 1978-06-01 Westinghouse Electric Corp ANALYZER FOR COMBUSTIBLE COMPONENTS IN A FUEL GAS ATMOSPHERE
US4071429A (en) * 1976-12-29 1978-01-31 Monsanto Company Electrolytic flow-cell apparatus and process for effecting sequential electrochemical reaction
US4267023A (en) * 1977-10-17 1981-05-12 Orion Research Incorporated Chemically integrating dosimeter and gas analysis methods
US4324257A (en) * 1978-02-20 1982-04-13 U.S. Philips Corporation Device for the transcutaneous measurement of the partial oxygen pressure in blood
US4334510A (en) * 1978-11-21 1982-06-15 Thomson-Csf Electrochemical sensor for measuring relative concentrations of reactive species in a fluid mixture and a system comprising said sensor, especially for regulation
US4324632A (en) * 1979-05-17 1982-04-13 City Technology Limited Gas sensor
EP0078627A1 (en) * 1981-10-19 1983-05-11 Westinghouse Electric Corporation Improved solid electrolyte gas sensing apparatus
US4563249A (en) * 1983-05-10 1986-01-07 Orbisphere Corporation Wilmington, Succursale De Collonge-Bellerive Electroanalytical method and sensor for hydrogen determination
US4808293A (en) * 1986-12-19 1989-02-28 Matsushita Electric Industrial Co., Ltd. Oxygen sensor and method of making such sensor
US5178744A (en) * 1988-10-31 1993-01-12 Fujikura Ltd. Oxygen sensor device
US5092980A (en) * 1990-02-23 1992-03-03 Dragerwerk Aktiengesellschaft Measuring apparatus for detecting gases
US5906718A (en) * 1995-04-21 1999-05-25 Mine Safety Appliances Company Electrochemical gas sensor for the detection of nitrogen dioxide
US5668302A (en) * 1995-05-24 1997-09-16 City Technology Limited Electrochemical gas sensor assembly
EP0756172A1 (en) * 1995-07-26 1997-01-29 Praxair Technology, Inc. Neural network compensation for sensors
US6404205B1 (en) * 1997-05-09 2002-06-11 Japan Storage Battery Co., Ltd. Method for testing the reliability of an electrochemical gas sensor
US20100136444A1 (en) * 2005-09-21 2010-06-03 Nash David A Electrical bridge for fuel cell plates
WO2017060380A1 (en) * 2015-10-09 2017-04-13 Flexenable Limited Sensing device and method of producing the same
CN108139353A (en) * 2015-10-09 2018-06-08 弗莱克因艾伯勒有限公司 Sensing device further and the method for manufacturing the sensing device further
CN108139353B (en) * 2015-10-09 2021-03-19 弗莱克因艾伯勒有限公司 Sensing device and method of manufacturing the same
US11029276B2 (en) 2015-10-09 2021-06-08 Flexenble Limited Sensing device

Similar Documents

Publication Publication Date Title
US3787308A (en) Oxygen sensor
US3325378A (en) Electrochemical method and apparatus for measuring hydrogen content
US4406770A (en) Gas sensor
US3260656A (en) Method and apparatus for electrolytically determining a species in a fluid
US3296113A (en) Gas-stream monitor
US3966579A (en) Apparatus for measuring alcohol concentrations
US4025412A (en) Electrically biased two electrode, electrochemical gas sensor with a H.sub.2
US4790925A (en) Electrochemical gas sensor
Yan et al. A solid polymer electrolyte-bases electrochemical carbon monoxide sensor
US3223597A (en) Method and means for oxygen analysis of gases
GB1340367A (en) Fluid analysis apparatus
EP0141282A1 (en) Method of and system for real time differential pulse detection
US3505195A (en) Electrode system for electro-chemical measurements in solutions
US3992153A (en) Dosimeter for oxides of nitrogen
Miura et al. An improved type of proton conductor sensor sensitive to H2 and CO at room temperature
US4948496A (en) Gas sensor
US3258415A (en) Oxygen analyzer and oxygen-depolarized cell therefor
CA2164438A1 (en) Gas detection, identification and elemental and quantitative analysis system
Kocache The measurement of oxygen on gas mixtures
EP0432962A2 (en) Flammable gas detection
CN109406614A (en) Hand-held oxygen detection instrument and its working method
US3247452A (en) Gas sensing device with a gasdepolarizable electrode
US2540674A (en) Apparatus for determining oxygen in gases
US2991412A (en) Oxygen analyzer
US3837808A (en) Method of analyzing oxygen

Legal Events

Date Code Title Description
AS Assignment

Owner name: CONGRESS FINANCIAL CORPORATION; A CORP OF CA.

Free format text: SECURITY INTEREST;ASSIGNOR:EXIDE CORPORATION;REEL/FRAME:004122/0001

Effective date: 19830322

AS Assignment

Owner name: NATIONAL BANK OF CANADA, A BANKING CORP. OF CANADA

Free format text: SECURITY INTEREST;ASSIGNOR:EXIDE CORPORATION;REEL/FRAME:004122/0122

Effective date: 19830322

AS Assignment

Owner name: EXIDE CORPORATION

Free format text: SECURITY AGREEMENT RECORDED MARCH 31, 1983, REEL 4122-FRAMES 001 TO 074 IS HEREBY TERMINATED;ASSIGNOR:CONGRESS FINANCIAL CORPORATION;REEL/FRAME:004747/0780

Effective date: 19870409

STCF Information on status: patent grant

Free format text: PATENTED FILE - (OLD CASE ADDED FOR FILE TRACKING PURPOSES)

AS Assignment

Owner name: CHEMICAL BANK, A NY BANKING CORPORATION

Free format text: SECURITY INTEREST;ASSIGNORS:EXIDE CORPORATION;GENERAL BATTERY CORPORATION;ESB PUERTO RICO CORP.;AND OTHERS;REEL/FRAME:005449/0001

Effective date: 19900831