pH and CO.sub.2 sensing device and method of making the same

• US 4,536,274 A
• Filed: 04/18/1983
• Issued: 08/20/1985
• Est. Priority Date: 04/18/1983
• Status: Expired due to Fees

• Current Assignee: BioSpecifics Technologies Corp. (Endo International PLC)
• Original Assignee: Diamond Shamrock Chemicals Co (Valero Energy Corporation)
• Inventors: Papadakis, Nicholas, Kalynchuk, Daniel G.
• Primary Examiner(s): Kaplan, G. L.
• Assistant Examiner(s): Nguyen, Nam X.
• Application Number:
  US06/486,024
• Time in Patent Office: 855 Days
• Field of Search: 204/415, 204/403, 204/416, 204/418, 204/430, 204/431, 204/433, 204/39, 204/56 R, 128/635, 29/570, 427/123, 427/124, 427/125, 324/438
• US Class Current: 204/433
• CPC Class Codes: A61B 5/14539 for measuring pH
• CPC Class Codes: A61B 5/14542 for measuring blood gases A61B5/14551 takes precedence
• CPC Class Codes: A61B 5/1477 non-invasive
• CPC Class Codes: G01N 27/4045 for gases other than oxygen
• CPC Class Codes: G01N 33/4925 measuring blood gas content, e.g. O2, CO2 , HCO3

Abstract

A transcutaneous blood carbon dioxide sensor together with a method for making such a sensor and for making electrodes used in the sensor. The sensor comprises a palladium/palladium oxide junction type electrode and a silver/silver halide junction type electrode applied to an electrically nonconductive substrate, partially coated with an insulative dielectric and partially coated with a polymeric membrane material including a bound electrolyte, the polymeric membrane material being permeable to carbon dioxide. The Pd/PD0 electrode was made cathodic prior to terminating the electro-oxidizing conditions.

Claims

1. A CO₂ gas sensor comprising:

an electrically nonconductive substrate;

a metal/metal oxide junction type active electrode including an active electrode metal, the active electrode metal being applied to the substrate by one of thick film and thin film techniques, and the active metal being then subjected to electro-oxidizing conditions for a period of time sufficient to oxidize a portion of the applied active electrode metal, the applied active electrode metal being made cathodic prior to discontinuance of the electro-oxidizing conditions;

a silver/silver halide junction type reference electrode, adheringly applied to the substrate;

an insulating, dielectric coating applied over at least portions of the substrate and electrodes;

and a polymeric membrane comprising a laminate of a hydrophobic polymeric material atop a hydrophilic membrane material applied over at least those portions of the electrodes not having the insulating dielectric coating applied thereto, the polymeric membrane being capable of relatively rapidly transmitting CO₂ thereacross, and the polymeric material including a liquid electrolyte bound by the polymeric membrane.

2. A method for making a solid state pH sensor comprising the steps of:

selecting an electrically nonconducting substrate formed from a material selected from a group consisting essentially of ceramics, refractories, thermoplastics, and thermosetting resins;

applying an active electrode metal to the substrate by one of thick and thin film techniques to form an electrode of desired physical configuration adhered to the substrate;

adheringly applying to the substrate a silver/silver halide junction type reference electrode;

oxidizing a portion of the active electrode metal by subjecting the active electrode metal to electro-oxidizing conditions for a period of time necessary to form a desired quantity of an oxide of the metal, the active electrode metal being made cathodic at least immediately prior to terminating the electro-oxidizing conditions; and

applying to at least portions of the electrodes and the substrate an insulating dielectric coating.

3. The method of claim 2, the active electrode metal being applied by thick film screen printing of a precursor compound including the metal onto the substrate and then sintering the applied precursor to provide an active electrode metal upon the substrate.

4. The method of claim 3, the substrate being alumina, wherein electro-oxidation is accomplished by making the active electrode metal anodic within a fused salt electrolyte consisting of NaNO₃ and LiCl salts under an impressed current of between about 0.1 milliamperes and 20.0 milliamperes per square centimeter of active electrode metal surface, followed by making the active electrode metal cathodic prior to removing the now active electrode from the fused salt electrolyte and including the step of:

applying to at least those portions of the electrode not having an applied coating of an insulating dielectric a polymeric membrane capable of binding a liquid electrolyte within the polymeric membrane.

5. The method of claim 2, the substrate being alumina, wherein electro-oxidation is accomplished by making the active electrode metal anodic within a fused salt electrolyte consisting of NaNO₃ and LiCl salts under an impressed current of between about 0.1 milliamperes and 20.0 milliamperes per square centimeter of active electrode metal surface, followed by making the active electrode metal cathodic prior to removing the now active electrode from the fused salt electrolyte and including the step of:

applying to at least those portions of the electrode not having an applied coating of an insulating dielectric a polymeric membrane capable of binding a liquid electrolyte within the polymeric membrane.

6. A pH sensor produced by the method set forth in claim 3.

7. A method for making a CO₂ gas sensor comprising the steps:

selecting an electrically nonconducting substrate formed from a material selected from a group consisting essentially of ceramics, refractories, thermoplastics, and thermosetting resins;

applying an active electrode metal to the substrate by one of thick and thin film techniques to form an electrode of desired physical configuration adhered to the substrate;

adheringly applying to the substrate a silver/silver halide junction type reference electrode;

applying to at least portions of the electrodes and the substrate an insulating dielectric coating;

oxidizing a portion of the active electrode metal by subjecting the active electrode metal to electro-oxidizing conditions for a period of time necessary to form a desired quantity of an oxide of the active electrode metal, the active electrode metal being made cathodic prior to terminating the electro-oxidizing conditions; and

applying to at least those portions of the resulting sensor not having an applied coating of an insulating dielectric a polymeric membrane comprising a laminate of a hydrophobic polymeric material atop a hydrophilic membrane material capable of binding a liquid electrolyte within the polymeric membrane, electro-oxidation being accomplished by making the active electrode metal anodic within a fused salt electrolyte consisting of NaNO₃ and LiCl salts under an impressed current of between about 0.1 milliamperes and 20.0 milliamperes per square centimeter of active electrode metal surface, followed by making the now active electrode cathodic prior to removing the active electrode from the fused salt electrolyte.

8. A method for making a transcutaneous blood CO₂ gas sensor comprising the steps:

selecting an electrically nonconducting substrate formed from alumina;

applying an active electrode metal to the substrate by one of thick and thin film techniques to form an electrode of desired physical configuration adhered to the substrate;

adheringly applying to the substrate a silver/silver halide junction type reference electrode;

applying to at least portions of the electrodes and the substrate an insulating dielectric coating;

oxidizing a portion of the active electrode metal by subjecting the active electrode metal to electro-oxidizing conditions for a period of time necessary to form a desired quantity of an oxide of the active electrode metal, the active electrode metal being made cathodic prior to terminating the electro-oxidizing conditions; and

applying to at least those portions of the resulting sensor not having an applied coating of an insulating dielectric a polymeric membrane comprising a laminate of a hydrophobic polymer material atop a hydrophilic membrane material capable of binding a liquid electrolyte within the polymeric membrane, and wherein electro-oxidation is accomplished by making the active electrode anodic within a fused salt electrolyte consisting of NaNO₃ and LiCl salts under an impressed current of between about 0.1 milliamperes and 20.0 milliamperes per square centimeter of active electrode metal surface, followed by making the now active electrode cathodic prior to removing the active electrode from the fused salt electrolyte.

9. The method of claim 8, the active electrode metal being applied by thick film screen printing of a precursor compound including the metal onto the substrate and then sintering the applied precursor to provide an active electrode metal upon the substrate.

10. A method for making a precious metal/precious metal oxide junction type electrode comprising the steps of:

selecting a precious metal electrode precursor the metal being selected from a group consisting of palladium, iridium, rhodium, ruthenium and osmium;

immersing at least a portion of the electrical precursor in a molten salt electrolyte;

making the electrode precursor anodic at an electrical current not exceeding about 20 milliamperes per square centimeter of immersed electrode precursor to form a desired quantity of the precious metal oxide; and

at least once making the electrode precursor cathodic prior to removal from the molten salt electrolyte at an electrical current not exceeding the current density while anodic.

11. A solid state pH sensor comprising:

an electrically nonconductive substrate;

a metal/metal oxide junction type active electrode including an active electrode metal, the active electrode metal being applied to the substrate by one of thick film and thin film techniques, and the active metal being then subjected to electro-oxidizing conditions for a period of time sufficient to oxidize a portion of the applied active electrode, the applied active electrode metal being made cathodic prior to discontinuance of the electro-oxidizing conditions;

a metal/metal halide junction type reference electrode, adheringly applied to the substrate; and

an insulating, dielectric coating applied over at least portions of the substrate and electrodes.

12. The sensor of claim 11 including a polymeric membrane capable of supporting hydrogen ion transport thereacross applied over at least those portions of the electrodes not having the insulating dielectric coating applied thereto.

13. The sensor of claim 11 wherein the metal/metal oxide electrode is palladium/palladium oxide and the metal/metal halide electrode is silver/silver halide.