Electrochemical sensors made from conductive polymer composite materials and methods of making same

• US 6,315,956 B1
• Filed: 03/16/1999
• Issued: 11/13/2001
• Est. Priority Date: 03/16/1999
• Status: Expired due to Term

• Current Assignee: Prysmian Power Cables and Systems USA LLC (Prysmian SPA)
• Original Assignee: Pirelli Cables And Systems, LLC
• Inventors: Foulger, Stephen H.
• Primary Examiner(s): Warden, Jill
• Assistant Examiner(s): SINES, BRIAN J
• Application Number:
  US09/268,884
• Time in Patent Office: 973 Days
• Field of Search: 73/310.2, 73/310.1, 422/98, 422/100, 422/102, 422/82.02, 525/106, 525/425, 528/411, 528/367, 428/323, 428/367, 526/279, 521/53, 521/54, 252/511, 264/105, 204/407, 204/421, 204/422, 205/783.5
• US Class Current: 422/98
• CPC Class Codes: G01N 27/126 comprising organic polymers
• CPC Class Codes: G01N 27/308 at least partially made of carbon
• CPC Class Codes: H01B 1/124 Intrinsically conductive polymers

Abstract

An electrochemical sensor which is tailored for sensitivity to specific chemical analytes by selecting proper constituents. The electrochemical sensor is comprised of an immiscible polymer blend of at least two polymers in which a conductive filler is dispersed in one of the polymers of the blend through a multiple percolation approach to compounding. When in the presence of a chemical analyte which is in either a liquid or vapor phase, one phase of the dual immiscible polymer blend swells, effecting a decrease in the conductivity, or increase in resistivity, of the polymer blend. The electrochemical sensor is reversible in that when the chemical analyte evaporates or is removed, the polymer blend returns to its original conductivity. With the multiple percolation approach it is possible to make a single composite material identifiably sensitive to various chemical analytes by incorporating several major phase materials into the immiscible polymer blend, each having an affinity for swelling for a different analyte. Further, the multiple percolation approach allows sensors to be made at extremely low cost.

Claims

1. A reversible electrochemical sensor for detecting the presence of chemical analytes comprising:

(a) a conductive polymer composite of an immiscible polymer blend, said blend comprising (1) a conductive filler material, (2) a minor phase material in which said conductive filler material is dispersed in an amount sufficient to generate a continuous conductive network in said minor phase material and forming a binary composite, and (3) a major phase material with an affinity for at least one analyte, said major phase material being a polymer which when mixed with said binary composite will not engage in electrostatic interactions that promote miscibility, said major phase material having said binary composite dispersed therein in an amount sufficient to generate a continuous conductive network in said major phase material and forming a conducive ternary composite having distinct co-continuous phases; and

(b) a pair of electrodes in electrical contact with said conductive ternary composite, wherein electrical properties of said conductive ternary composite undergo a reversible change when in proximity to at least one analyte.

2. The electrochemical sensor of claim 1, wherein the electrical properties of said conductive ternary composite are selected from the group comprising resistance, conductance, and capacitance.

3. The electrochemical sensor of claim 1, wherein said conductive filler material comprises between about 0.001 percent by weight and about 25 percent by weight of the total conductive polymer composite weight.

4. The electrochemical sensor of claim 1, wherein said amount of conductive filler material dispersed in said minor phase material is not more than 0.5% by weight greater than the amount sufficient to generate a continuous conductive network in said minor phase material;

and wherein said amount of binary composite dispersed in said major phase material is not more than 1% by weight greater than the amount sufficient to generate a continuous conductive network in said major phase material.

5. The electrochemical sensor of claim 1, wherein said amount of conductive filler material dispersed in said minor phase material is not more than 1% by weight greater than the amount sufficient to generate a continuous conductive network in said minor phase material;

and wherein said amount of binary composite dispersed in said major phase material is not more than 2% by weight greater than the amount sufficient to generate a continuous conductive network in said major phase material.

6. The electrochemical sensor of claim 1, wherein said amount of conductive filler material dispersed in said minor phase material is not more than 2% by weight greater than the amount sufficient to generate a continuous conductive network in said minor phase material;

and wherein said amount of binary composite dispersed in said major phase material is not more than 2% by weight greater than the amount sufficient to generate a continuous conductive network in said major phase material.

7. The electrochemical sensor of claim 1, wherein said amount of conductive filler material dispersed in said minor phase material is not more than 5% by weight greater than the amount sufficient to generate a continuous conductive network in said minor phase material;

and wherein said amount of binary composite dispersed in said major phase material is not more than 5% by weight greater than the amount sufficient to generate a continuous conductive network in said major phase material.

8. The electrochemical sensor of claim 1, wherein said conductive filler material is selected from the group consisting of carbon black, graphite, metallic particles, carbon fibers, intrinsically conductive polymers, fullerenes, nanotubes, whiskers, and combinations thereof.

9. The electrochemical sensor of claim 1, wherein said minor phase material has a crystallinity of about 20% to about 80%.

10. The electrochemical sensor of claim 1, wherein said minor phase material is a semicrystalline polymer and said major phase material has a crystallinity of about 20% to about 80% such that said conductive polymer composite physically crosslinks through crystalline regions.

11. The electrochemical sensor of claim 1, wherein said conductive polymer composite is exposed to β

or γ

radiation for a sufficient time to effect crosslinking of the composite.

12. The electrochemical sensor of claim 1, wherein a hydrolyzable group is grafted onto said major phase material prior to dispersing said minor phase material therein, such that said conductive polymer composite will crosslink on exposure to moisture.

13. The electrochemical sensor of claim 12, wherein said major phase material is a commercially available copolymer which contains a hydrolyzable functionality as part of the copolymer backbone.

14. The electrochemical sensor of claim 1, wherein a hydrolyzable copolymer is created by grafting an unsaturated moiety containing one or more hydrolyzable functionalities to the backbone of said major phase material prior to dispersing said minor phase material in said major phase material.

15. The electrochemical sensor of claim 1, wherein an organic peroxide is added to said major phase material prior to dispersion of said minor phase material, therein, thereby effecting crosslinking with the decomposition of the peroxide and subsequent generation of free radicals at elevated temperatures.

16. The electrochemical sensor of claim 1, wherein said minor phase material is high density polyethylene and said major phase material is comprised of a poly(ethylene-co-vinyl acetate).

17. The electrochemical sensor of claim 16, wherein vinyl acetate content comprises from about 9% to about 45% by weight of said poly(ethylene-co-vinyl acetate), such that an affinity of said poly(ethylene-co-vinyl acetate) for at least one analyte is selectively adjusted by varying said vinyl acetate content of said poly(ethylene-co-vinyl acetate).

18. The electrochemical sensor of claim 1, further comprising means for crosslinking said conductive polymer composite.

19. The electrochemical sensor of claim 1, further comprising:

a second major phase material, said second major phase material having an affinity for a second analyte, wherein said conductive ternary composite is dispersed in an amount sufficient to generate a continuous conductive network in said second major phase material, said second major phase material being selected from that group of polymers which when mixed with said conductive ternary composite will not engage in electrostatic interactions that promote miscibility with said minor phase material or with said major phase material, forming a conductive quaternary composite having distinct co-continuous phases, wherein electrical properties of said conductive quaternary composite undergo a reversible change when in proximity to said second analyte.

20. The electrochemical sensor of claim 19 wherein the electrical properties of said conductive quaternary composite are selected from the group comprising resistance, conductance, and capacitance.

21. The electrochemical sensor of claim 19, further comprising means for crosslinking said conductive quaternary composite.

22. The electrochemical sensor of claim 19, further comprising one or more additional major phase materials, each of said additional major phase materials being polymers having an affinity for additional analytes, said additional major phase materials being polymers which when mixed with each other, with said major phase material, with said second major phase material, and with said minor phase material will not engage in electrostatic interactions that promote miscibility, forming a conducting multi-phase composite having distinct co-continuous phases, wherein the conductivity of said conducting multi-phase composite undergoes a reversible change when in proximity to one of said additional analytes.

23. The electrochemical sensor of claim 22, further comprising means for crosslinking said conducting multi-phase composite.

24. The electrochemical sensor of claim 1, wherein said conductive polymer composite further comprises a material selected from the group consisting of antioxidants, nucleating agents, coupling agents, ultraviolet absorbers, ultraviolet stabilizers, pigments, dyes, reinforcing fillers, slip agents, plasticizers, processing aids, lubricants, viscosity control agents, tackifiers, anti-blocking agents, surfactants, extender oils, metal deactivators, voltage stabilizers, flame retardant fillers, cross-linking agents, boosters, catalysts, smoke suppressants, and combinations thereof in the amount of about 0.05% by weight to about 50% by weight of said conductive polymer composite.

25. A method of producing a reversible electrochemical sensor for detecting the presence of chemical analytes comprising:

mixing a minor phase polymer having a melting temperature at a temperature greater than or equal to said melting temperature of said minor phase polymer;

mixing a conductive filler with said minor phase polymer in an amount greater than or equal to an amount required to generate a continuous conductive network in said minor phase polymer for a time and at a sufficient speed to insure a uniform distribution of said conductive filler in said minor phase polymer, thereby forming a binary composite having a melting temperature;

mixing a major phase material having a melting temperature with said binary composite in a mixer preheated to at least the melting temperature of said major phase material and the melting temperature of said binary composite, for a time and at a sufficient speed to insure a uniform distribution of said binary composite in said major phase material, such that a weight ratio of said binary composite to said major phase material is sufficient for said binary composite to be equal to or greater than an amount required to generate a continuous conductive network in said major phase material, said major phase material being selected from that group of polymers which when mixed with said binary composite will not engage in electrostatic interactions which promote miscibility, such that a conductive ternary composite with co-continuous phases is formed; and

securing a pair of electrodes to said conductive ternary composite, said pair of electrodes being in electrical contact with said conductive ternary composite.

26. The method of claim 25, further comprising annealing said binary composite, thereby increasing the crystalline phase and resulting in a lower percolation threshold for the binary composite, thereby reducing the total amount of required conductive filler in the total composite.

27. The method of claim 25, further comprising optimizing the surface area to volume ratio of said binary composite prior to mixing with said major phase material, thereby lowering the percolation threshold necessary to generate a continuous conductive network.

28. The method of claim 25, further comprising:

crosslinking said conductive ternary composite.

29. The method of claim 25 further comprising:

annealing said conductive ternary composite prior to securing said pair of electrodes, thereby increasing the conductivity of said conductive ternary composite.

30. The method of claim 25 further comprising:

mixing a second major phase material having a melting temperature with said conductive ternary composite in said mixer preheated to above the melting temperature of said second major phase material and said conductive ternary composite, for a time and at a sufficient speed to insure a uniform distribution of said conductive ternary composite in said second major phase material, such that a weight ratio of said conductive ternary composite to said second major phase material is sufficient for said conductive ternary composite to be equal to or greater than an amount required to generate a continuous conductive network in said second major phase material, said second major phase material being selected from that group of polymers which when mixed with said conductive ternary composite will not engage in electrostatic interactions which promote miscibility with said binary composite or with said major phase material, such that a conductive quaternary composite with distinct co-continuous phases is formed, prior to securing said pair of electrodes.

31. The method of claim 30, further comprising:

annealing said conductive quaternary composite, said conductive ternary composite, and/or said binary composite thereby increasing the conductivity of said composite.

32. The method of claim 30, further comprising:

crosslinking said conductive quaternar composite.

33. The method of claim 30, further comprising the additional steps of mixing additional major phase materials with said conductive quaternary composite in a mixer preheated to above the melting temperature of each additional major phase material, said additional major phase materials being polymers which when mixed with each other, said second major phase material, said major phase material, said minor phase polymer and said conductive filler will not engage in electrostatic interactions that promote miscibility, said additional major phase materials each having an affinity for additional analytes, such that a multi-phase immiscible conducting polymer composite having distinct co-continuous phases is formed which undergoes a reversible change when in proximity to each of said additional analytes.

34. The method of claim 33 further comprising crosslinking said multi-phase immiscible conducting polymer composite.

35. The method of claim 25, further comprising:

adding material selected from the group consisting of antioxidants, nucleating agents, coupling agents, ultraviolet absorbers, ultraviolet stabilizers, pigments, dyes, reinforcing fillers, slip agents, plasticizers, processing aids, lubricants, viscosity control agents, tackifiers, anti-blocking agents, surfactants, extender oils, metal deactivators, voltage stabilizers, flame retardant fillers, boosters, catalysts, smoke suppressants, and combinations thereof to said conductive ternary composite in the amount of about 0.05% by weight to about 50% by weight of said conductive ternary composite.