Conductive polymer composite materials and methods of making same

• US 6,197,219 B1
• Filed: 05/07/1999
• Issued: 03/06/2001
• Est. Priority Date: 07/10/1998
• Status: Expired due to Term

• Current Assignee: Prysmian Power Cables and Systems USA LLC (Prysmian SPA)
• Original Assignee: Pirelli Cables And Systems, LLC (Prysmian SPA)
• Inventors: Foulger, Stephen H.
• Primary Examiner(s): Gupta, Yogendra
• Assistant Examiner(s): Hamlin, Derrick G.
• Application Number:
  US09/307,057
• Time in Patent Office: 669 Days
• Field of Search: 252/500, 252/510, 252/511, 252/519.32, 252/518.1, 174/25.R, 174/25.C, 174/36, 174/68.1, 174/102.R
• US Class Current: 252/500
• CPC Class Codes: C08K 3/04 Carbon
• CPC Class Codes: C08K 3/08 Metals
• CPC Class Codes: C08K 7/06 Elements
• CPC Class Codes: H01B 1/20 Conductive material dispersed in non-conductive organic material organic macromolecular compounds or compositions C08
• CPC Class Codes: H01B 1/22 the conductive material comprising metals or alloys
• CPC Class Codes: H01B 1/24 the conductive material comprising carbon-silicon compounds, carbon or silicon

Abstract

A conductive polymer composite material comprises: a minor phase material comprising a semicrystalline polymer; a conductive filler material dispersed in said minor phase material in an amount sufficient to be equal to or greater than an amount required to generate a continuous conductive network in said minor phase material; and a major phase material, said major phase material being a polymer which when mixed with said minor phase material will not engage in electrostatic interactions that promote miscibility, said major phase material having said minor phase material dispersed therein in an amount sufficient to be equal to or greater than an amount required to generate a continuous conductive network in said major phase material, forming a (semi)conductive ternary composite having distinct co-continuous phases.

Claims

1. A conducting polymer composite material comprising:

a minor phase material comprising a semicrystalline polymer having a crystallinity from greater than 30% to about 80% and having a solubility parameter, δ

_A;

a conductive filler material dispersed in said minor phase material in an amount which is at or just exceeds the percolation threshold and sufficient to generate a continuous conductive network in said minor phase material; and

a major phase material having a solubility parameter, δ

_B, said major phase material being a polymer which when mixed with said minor phase material will not engage in electrostatic interactions that promote miscibility, said major phase material having said minor phase material dispersed therein in an amount which is at or just exceeds the percolation threshold and sufficient to generate a continuous conductive network in said major phase material, forming a (semi)conductive ternary composite having distinct co-continuous phases which meets the following criteria for immiscibility, 7≧

(δ

_A--δ

_B)²≧

0.

2. The conducting polymer composite material of claim 1, wherein said minor phase material with conductive filler material dispersed therein has a volume resistivity of about ≦

10⁶ Ω

•

cm; and

said ternary composite has a volume resistivity of about ≦

10⁶Ω

•

cm.

3. The conducting polymer composite material of claim 1, wherein said minor phase material with conductive filler material dispersed therein has a volume resistivity of about ≧

10³ Ω

•

cm; and

said ternary composite has a volume resistivity of about ≦

10³ Ω

•

cm.

4. The conducting polymer composite material of claim 1, wherein said conductive filler material comprises about ≦

10 percent by weight of total conducting polymer composite weight.

5. The conducting polymer composite material of claim 1, wherein said conductive filler material is selected from the group consisting of carbon black, graphite, metallic particles, intrinsically conductive polymers, carbon fibers, and mixtures thereof.

6. The conducting polymer composite material of claim 1, wherein said conductive filler material is metallic particles and said conductive filler material comprises about ≧

85 percent by weight of total conducting polymer composite weight.

7. The conducting polymer composite material of claim 1, wherein said semicrystalline polymer is high density polyethylene.

8. The conducting polymer composite material of claim 1, wherein said major phase material is comprised of a poly(ethylene-co-vinyl acetate).

9. The conducting polymer composite material of claim 8, wherein said poly(ethylene-co-vinyl acetate) has a vinyl acetate content of greater than about 40% by weight.

10. The conducting polymer composite material of claim 1 wherein the composite material is an electrochemical sensor, a semiconductive cable jacket, a positive temperature coefficient device, a temperature sensor, a strand filling compound for electrical power cables, a thermoplastic semiconductive shield for conductor shields and insulation shields on electrical cable, an electrothermal sensor, an electrical shield, high permittivity devices, static charge dissipative flooring or static charge dissipative packaging.

11. The conducting polymer composite material of claim 1, further comprising a material selected from the group consisting of an antioxidant, a nulceating agent, and mixtures thereof.

36. The method of claim 11, further comprising:

repeating the steps of claim 33 with additional major phase materials, 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 the promote miscibility, such that a multi-phase composite material having distinct co-continuous phases is formed.

12. A conducting polymer composite material comprising:

a minor phase material comprising a semicrystalline polymer;

a conductive filler material dispersed in said minor phase material in an amount which is at or just exceeds the percolation threshold and sufficient to generate a continuous conductive network in said minor phase material;

a major phase material, said major phase material being a polymer which when mixed with said minor phase material will not engage in electrostatic interactions that promote miscibility, said major phase material having said minor phase material dispersed therein in an amount which is at or just exceeds the percolation threshold and sufficient to generate a continuous conductive network in said major phase material, forming a (semi)conductive ternary composite having distinct co-continuous phases; and

a second major phase material, wherein said ternary composite is dispersed in the second major phase material in an amount which is at or just exceeds the percolation threshold and sufficient for said ternary composite to be continuous within said second major phase material, said second major phase material being selected from a group of polymers which when mixed with said ternary composite will not engage in electrostatic interactions that promote miscibility with said minor phase material or said major phase material, forming a (semi)conductive quaternary composite having distinct co-continuous phases.

13. The conducting polymer composite material of claim 12, further comprising additional major phase materials, 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, such that a multi-phase composite material having distinct co-continuous phases is formed.

14. The conducting polymer composite material of claim 12, wherein the composite material is an electrochemical sensor, a semiconductive cable jacket, a positive temperature coefficient device, a temperature sensor, a strand filling compound for electrical power cables, a thermoplastic semiconductive shield for conductor shields and insulation shields on electrical cable, an electrothermal sensor, an electrical shield, high permittivity devices, static charge dissipative flooring or static charge dissipative flooring.

15. The conducting polymer composite material of claim 12, wherein said minor phase material with conductive filler material dispersed therein has a volume resistivity of about ≦

10⁶ Ω

•

cm and said ternary composite has a volume resistivity of about ≦

10⁶Ω

•

cm.

16. The conducting polymer composite material of claim 12, wherein said minor phase material with conductive filler material dispersed therein has a volume resistivity of about ≦

10³Ω

•

cm and said ternary composite has a volume resistivity of about ≦

10³Ω

•

cm.

17. The conducting polymer composite material of claim 12, wherein said conductive filler material comprises about ≦

10 percent by weight of total conducting polymer composite weight.

18. The conducting polymer composite material of claim 13, wherein said conductive filler material is selected from the group consisting of carbon black, graphite, metallic particles, intrinsically conductive polymers, carbon fibers, and mixtures thereof.

19. The conducting polymer composite material of claim 13, wherein said conductive filler material is metallic particles and said conductive filler comprises about ≧

85 percent by weight of total conducting polymer composite weight.

20. The conducting polymer composite material of claim 13, wherein said semicrystalline polymer is high density polyethylene.

21. The conducting polymer composite material of claim 13, wherein said major phase material is comprised of a poly(ethylene-co-vinyl acetate).

22. The conducting polymer composite material of claim 21, wherein said poly(ethylene-co-vinyl acetate) has a vinyl acetate content of greater than about 40% by weight.

31. The method of claim 20 wherein said poly(ethylene-co-vinyl acetate) has a vinyl acetate content of greater than about 40% by weight.

23. A conducting polymer composite material comprising:

a minor phase material comprising a semicrystalline polymer having a crystallinity from about 70% to about 80% and having a solubility parameter, δ

_A;

a conductive filler material dispersed in said minor phase material in an amount which is at or just exceeds the percolation threshold and sufficient to generate a continuous conductive network in said minor phase material; and

a major phase material having a solubility parameter, δ

_B, said major phase material being a polymer which when mixed with said minor phase material will not engage in electrostatic interactions that promote miscibility, said major phase material having said minor phase material dispersed therein in an amount which is at or just exceeds the percolation threshold and sufficient to generate a continuous conductive network in said major phase material, forming a (semi)conductive ternary composite having distinct co-continuous phases which meets the following criteria for immiscibility,

24. A method of producing a conducting polymer composite material comprising the steps of:

mixing a semicrystalline polymer having a melting temperature, a crystallinity from about 30% to about 80%, and a solubility parameter δ

_A at a temperature above the melting temperature of said semicrystalline polymer;

adding a conductive filler material to said mixing semicrystalline polymer in an amount ≧

an amount required to generate a continuous conductive network in said semicrystalline polymer;

mixing said conductive filler material and said semicrystalline polymer for a time and at a speed sufficient to insure a uniform distribution of said conductive filler in said semicrystalline polymer, thereby forming a binary composite having a melting temperature; and

mixing a major phase material having a solubility parameter δ

_B and having a melting temperature with said binary composite at a temperature above the melting temperature of said major phase material, for a time and at a speed sufficient 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 ≧

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 that promote miscibility, such that a (semi)conductive ternary composite with distinct co-continuous phases is formed and which meets the following criteria for immiscibity, 7≧

(δ

_A-δ

_B)²≧

0.

25. The method of claim 24, further comprising the step of:

annealing said ternary composite, thereby coarsening morphology of said ternary composite.

26. The method of claim 24, further comprising:

annealing said binary composite to below the melting temperature of the binary composite prior to mixing said major phase material with said binary composite, said major phase material having a melting temperature less than the melting temperature of said binary composite; and

mixing said major phase material and said binary composite at a temperature below said melting temperature of said binary composite.

27. The method of claim 24, further comprising:

extruding said binary composite into threadlike structures prior to mixing said major phase material with said binary composite, said major phase material having a melting temperature less than the melting temperature of the binary composite; and

mixing said major phase material and said extruded threadlike structures of binary composite at a temperature below said melting temperature of said binary composite.

28. The method of claim 24, further comprising:

pulverizing said binary composite prior to mixing said major phase material with said binary composite, said major phase material having a melting temperature less than the melting temperature of the binary composite; and

mixing said major phase material and said pulverized binary composite at a temperature below said melting temperature of said binary composite.

29. The method of claim 24, wherein said conductive filler material is selected from the group of consisting of carbon black, graphite, metallic particles, intrinsically conductive polymers, carbon fibers and mixtures thereof.

30. The method of claim 24, wherein said major phase material is comprised of a poly(ethylene-co-vinyl acetate).

32. The method of claim 24, wherein the conducting polymer composite material further comprises a material selected from the group consisting of an antioxidant, a nucleating agent, and mixtures thereof.

33. A method of producing a conducting polymer composite material comprising the steps of:

mixing a semicrystalline polymer having a melting temperature at a temperature above the melting temperature of said semicrystalline polymer;

adding a conductive filler material to said mixing semicrystalline polymer in an amount ≧

an amount required to generate a continuous conductive network in said semicrystalline polymer;

mixing said conductive filler material and said semicrystalline polymer for a time and at a speed sufficient to insure a uniform distribution of said conductive filler in said semicrystalline polymer, thereby forming a binary composite having a melting temperature; and

mixing a major phase material having a melting temperature with said binary composite at a temperature above the melting temperature of said major phase material, for a time and at a speed sufficient 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 ≧

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 that promote miscibility, such that a (semi)conductive ternary composite with distinct co-continuous phases is formed; and

mixing a second major phase material having a melting temperature with said ternary composite at a temperature above the melting temperature of said second major phase material, for a time and at a speed to insure a uniform distribution of said ternary composite in said second major phase material, such that a weight ratio of said ternary composite to said second major phase material is sufficient for said ternary composite to be ≧

an amount required to generate a continuous conductive network in said second major phase material, said second major phase material being selected from a group of polymers which when mixed with said ternary composite will not engage in electrostatic interactions that promote miscibility with said binary composite or said major phase material, such that a (semi)conductive quaternary composite with distinct co-continuous phases is formed.

34. The method of claim 33, further comprising:

annealing said quaternary composite, thereby coarsening morphology of said quaternary composite.

35. A The method of claim 34, wherein said threadlike structures are about 2 mm long and about 0.25 mm in diameter.

37. A method of producing a conducting polymer composite material comprising:

mixing a semicrystalline minor phase polymer material having a crystallinity from about 30% to about 80% and a solubility parameter δ

_A with a conductive filler material, the conductive filler material being in an amount sufficient to be equal to or greater than an amount required to generate a continuous conductive network within the minor phase polymer material, thereby forming a binary composite;

mixing the binary composite with a major phase polymer material having a solubility parameter δ

_B to form a ternary composite having distinct phases; and

annealing the ternary composite to coarsen the morphology and thereby further increase conductivity of the composite material, said major phase polymer material being selected from a group of polymers which when mixed with said binary composite will not engage in electrostatic interactions that promote miscibility, such that a (semi)conductive ternary composite with distinct co-continuous phases is formed and which meets the following criteria for immiscibility, 7≧

(δ

_A-δ

_B)₂≧

0.

38. A method of producing a conducting polymer composite material comprising:

mixing a semicrystalline minor phase polymer material having a melting temperature, a crystallinity from about 30% to about 80% and a solubility parameter δ

_A, with a conductive filler material, the conductive filler material being in an amount sufficient to be equal to or greater than an amount required to generate a continuous conductive network within the minor phase polymer material, thereby forming a binary composite;

annealing the binary composite; and

mixing the binary composite with a major phase polymer material at a temperature below the melting temperature of the binary composite, said major phase polymer material being selected from a group of polymers which when mixed with said binary composite will not engage in electrostatic interactions that promote miscibility, thereby forming a (semi)conductive ternary composite having distinct co-continuous phases and which meets the following criteria for immiscibility,

39. A method of producing a conducting polymer composite material comprising:

mixing a semicrystalline minor phase polymer material with a conductive filler material, the conductive filler material being in an amount sufficient to be equal to or greater than an amount required to generate a continuous conductive network within the minor phase polymer material, thereby forming a binary composite;

mixing the binary composite with a major phase polymer material to form a ternary composite;

mixing the ternary composite with a second major phase polymer material to form a semiconductive quaternary composite; and

annealing the quaternary composite to coarsen the morphology and thereby further increase the conductivity of the composite material, said major phase polymer material being selected from a group of polymers which when mixed with said binary composite will not engage in electrostatic interactions that promote miscibility, such that a (semi)conductive ternary composite with distinct co-continuous phases is formed.