EP0971368A1 - Halbleitermaterial, Verfahren zur Herstellung desselben und damit ummanteltes Kabel - Google Patents

Halbleitermaterial, Verfahren zur Herstellung desselben und damit ummanteltes Kabel Download PDF

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EP0971368A1
EP0971368A1 EP99305465A EP99305465A EP0971368A1 EP 0971368 A1 EP0971368 A1 EP 0971368A1 EP 99305465 A EP99305465 A EP 99305465A EP 99305465 A EP99305465 A EP 99305465A EP 0971368 A1 EP0971368 A1 EP 0971368A1
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Prior art keywords
phase material
composite
semiconductive
minor
major phase
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French (fr)
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EP0971368B1 (de
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Stephen H. Foulger
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Pirelli Communications Cables and Systems USA LLC
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Pirelli Cables and Systems LLC
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Priority claimed from US09/113,914 external-priority patent/US6514608B1/en
Priority claimed from US09/307,735 external-priority patent/US6189211B1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys

Definitions

  • the present invention relates generally to cables, and more particularly to compositions suitable for semiconductive jackets especially for medium and high voltage power cables and cables jacketed therewith.
  • Electric power cables for medium and high voltages typically include a core electrical conductor, an overlaying semiconductive shield, an insulation layer formed over the semiconductive shield, an outermost insulation shield, and some type of metallic component.
  • the metallic component may include, for example, a lead sheath, a longitudinally applied corrugated copper tape with overlapped seam, or helically applied wires, tapes, or flat strips.
  • Electric power cables for medium and high voltage applications also typically include an overall extruded plastic jacket which physically protects the cable thereby extending the useful life of the cable.
  • the afore-described overall jacket may be insulating or semiconducting. If the overall jacket is insulating, it may overlay or encapsulate the metallic component of the cable as discussed in the September/October 1995 Vol. 11, No. 5, IEEE Electrical Insulation Magazine article, entitled, Insulating and Semiconductive Jackets for Medium and High Voltage Underground Power Cable Applications, the contents of which are herein incorporated by reference.
  • semiconductive jackets are advantageously grounded throughout the length of the cable and therefore do not need periodic grounding previously described. Accordingly, semiconductive jackets are only grounded at the transformer and at the termination.
  • ICEA Insulated Cable Engineers Association
  • ASTM American Society for Testing and Materials
  • Prior art polymer compounds used in the role of a semiconductive jackets are normally thermoplastic and get their conductivity by use of a large weight percentage of a conductive filler material, usually conductive grades of carbon black, to incur a high level of conductivity (or low level of resistivity), to the compound.
  • the National Electrical Safety Code (Section 354D2-c) requires a radial resistivity of the semiconducting jacket to be not more than 100 ⁇ m and shall remain essentially stable in service.
  • Prior art compositions required loadings of conductive filler material of at least about 15% to 60% by weight to achieve this criteria. These high levels of conductive filler material inherently add significantly to the cost of such compositions, inhibit the ease of extrusion of the jacketing composition, and decrease the mechanical flexibility of the resultant cable.
  • Percolation theory is relatively successful in modeling the general conductivity characteristics of conducting polymer composite (CPC) materials by predicting the convergence of conducting particles to distances at which the transfer of charge carriers between them becomes probable.
  • the percolation threshold (p c ) which is the level at which a minor phase material is just sufficiently incorporated volumetrically into a major phase material resulting in both phases being co-continuous, that is, the lowest concentration of conducting particles needed to form continuous conducting chains when incorporated into another material, can be determined from the experimentally determined dependence of conductivity of the CPC material on the filler concentration.
  • the present invention provides a conductive polymer composite (CPC) material for semiconductive jackets for cables which has a significant reduction in conductive filler content while maintaining the required conductivity and mechanical properties specified by industry by selecting materials and processing approaches to reduce the percolation threshold of the conductive filler in the composite, while balancing the material selection with the industry required mechanical properties of the semiconductive jacket.
  • CPC conductive polymer composite
  • the present inventive semiconductive jackets for cables share certain attributes with U.S. Application Serial No. 09/113,963, entitled, Conductive Polymer Composite Materials And Methods of Making Same, filed on an even date with the parent of this application, July 10, 1998, by the same applicant, the contents of which are herein incorporated by reference. That is, the semiconductive jacket materials of the present invention are based on immiscible polymer blends wherein the immiscibility is exploited to create semiconductive compounds with low content conductive filler through a multiple percolation approach to network formation.
  • the conductive filler material content can be reduced to about 10% by weight of the total composite or less, depending on the conductive filler material itself and the selection of major and minor phase materials, without a corresponding loss in the conductivity performance of the compound.
  • the rheology of the melt phase of the inventive material will more closely follow an unfilled system due to the reduction of the reinforcing conductive filler content thereby increasing the ease of processing the material.
  • the physics of network formation of a minor second phase material in a differing major phase is effectively described by percolation theory as discussed heretofore.
  • the "percolation threshold" (p c ) is the level at which a minor phase material is just sufficiently incorporated volumetrically into a major phase material resulting in both phases being co-continuous, that is, the lowest concentration of conducting particles needed to form continuous conducting chains when incorporated into another material.
  • a minor second phase material in the form of nonassociating spheres, when dispersed in a major phase material must often be in excess of approximately 16% by volume to generate an infinite network.
  • This 16 volume % threshold which is exemplary for spheres, is dependent on the geometry of the conductive filler particles, (i.e. the surface area to volume ratio of the particle) and may vary with the type of filler.
  • the addition of a single dispersion of conductor filler particles to a single major phase is termed "single percolation". It has been found that by altering the morphology of the minor/major phase a significant reduction in percolation threshold can be realized.
  • the present invention exploits these aspects of percolation theory in developing very low conductive filler content semiconductive jacket materials for cables.
  • a method requiring an immiscible blend of at least two polymers that phase separate into two continuous morphologies is employed.
  • the concentration of conductive filler can be concentrated above the percolation threshold required to generate a continuous conductive network in the minor polymer phase while the total concentration of conductive filler in the volume of the combined polymers is far below the threshold if the filler was dispersed uniformly throughout both phases.
  • the concentration is conductive. This approach employs multiple percolation due to the two levels of percolation that are required: percolation of conductive dispersion in a minor phase and percolation of a minor phase in a major phase.
  • the filler particles are rejected from the crystalline regions into the amorphous regions upon recrystallization, which accordingly decreases the percolation threshold.
  • using a polymer blend with immiscible polymers which results in dual phases as the matrix in CPC materials promotes phase inhomogeneities and lowers the percolation threshold.
  • the conductive filler is heterogeneously distributed within the polymers in this latter example.
  • either one of the two polymer phases is continuous and conductive filler particles are localized in the continuous phase.
  • the two phases are co-continuous and the filler is preferably in the minor phase or at the interface.
  • the present invention concentrates primarily on two aspects of percolation phenomenon: the interaction of the conductive dispersion in the minor phase, and the interaction of the minor phase with the major phase. Further, the foregoing approach as disclosed in the afore-referenced U.S. Application Serial No. 09/113,963, entitled, Conductive Polymer Composite Materials and Methods of Making Same may be employed and has been optimized and balanced for semiconductive jacket applications.
  • a semiconductive jacket material for jacketing a cable 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 semiconductive jacket material of a ternary composite having distinct co-continuous phases.
  • the ternary composite has a volume resistivity of about ⁇ 100 ⁇ m, an unaged tensile strength of at least about 1200 psi, a tensile strength of at least about 75% of said unaged tensile strength after aging in an air oven at 100°C for 48 hours, an aged and unaged elongation at break of at least about 100%, a heat distortion at 90°C of at least about -25%, and a brittleness temperature of about ⁇ -10°C.
  • the conductive filler material comprises about ⁇ 10 percent by weight of total conducting polymer composite weight.
  • the semiconductive jacket material further comprises a second major phase material, wherein said ternary composite is dispersed in an amount 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 semiconductive jacket material of a quaternary composite having distinct co-continuous phases.
  • a method of producing a semiconductive jacket material for jacketing a cable comprises: mixing a semicrystalline polymer having a melting temperature in a mixer, said mixer preheated to above the melting temperature of said semicrystalline polymer; adding a conductive filler material to said semicrystalline polymer in said mixer in an amount ⁇ an amount required to generate a continuous conductive network in said semicrystalline polymer; mixing said conductive filler material and said semicrystalline 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; and mixing a major phase material having a melting temperature with said binary composite in said mixer preheated to 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
  • a method of producing a semiconductive jacket material for jacketing a cable comprises: 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 semiconductive jacket material of a ternary composite having distinct phases; and annealing the ternary composite to coarsen the morphology and thereby further increase conductivity of the jacket 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 semiconductive ternary composite with distinct co-continuous phases is formed.
  • a method of producing a semiconductive jacket material for jacketing a cable comprises: mixing a semicrystalline minor phase polymer material having a melting temperature 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 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 semiconductive jacket material of a ternary composite having distinct co-continuous phases.
  • a method of producing a semiconductive jacket material for jacketing a cable comprises: 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 jacket material of a quaternary composite having distinct phases; and annealing the quaternary composite to coarsen the morphology and thereby further increase the conductivity of the jacket 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 semiconductive ternary composite with distinct co-continuous phases is formed.
  • a cable comprises at least one transmission medium and a semiconductive jacket surrounding said transmission medium, said semiconductive jacket comprising: 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 semiconductive jacket material of a ternary composite having distinct co-continuous phases.
  • the superior results of the present invention may be achieved by allowing the conductive filler material to reside in a minor phase of the immiscible blend; the minor phase being a semicrystalline polymer having a relatively high crystallinity, such as between about 30% and about 80%, and preferably about ⁇ 70%, thereby causing the conductive filler aggregates to concentrate in amorphous regions of the minor phase or at the interface of the continuous minor and major phases.
  • Annealing processes of the composite at different points in the mixing process or modifying the morphology of the minor phase can further increase the crystalline phase or further coarsen the morphology of the blend and thereby improve the conductive network.
  • the minor and major phase materials in order that a favorable phase morphology, that is, phase separation, develops between minor and major phase materials, the minor and major phase materials must be such that when mixed, the minor and major phase polymeric materials do not engage in electrostatic interactions that promote miscibility resulting in a negative enthalpy of mixing. Thus, hydrogen bonding does not occur between any of the phases and there is phase separation between all of the phases.
  • the solubility parameter difference ( ⁇ A - ⁇ B ) of the minor and major phase materials in the ternary composites of the present invention meet the following criteria for immiscibility: U L ⁇ ( ⁇ A - ⁇ B ) 2 ⁇ 0 Where,
  • An advantage of the present invention includes the reduction of conductive filler material content in a semiconductive cable jacket to less than about 6 weight percent of total composite weight without a corresponding loss in the conductivity performance of the jacket.
  • Yet another advantage of the present invention is the ability to produce a semiconductive cable jacket which satisfies the ICEA S-94-649-1997 "Semiconducting Jacket Type 1" specification requirements.
  • Yet another advantage is the cost reduction due to the reduced conductive filler content and ease of processing over conventional semiconducting jackets.
  • Semiconductive jacket material for cables having good conductivity with significant reduction of conductive filler content of the present invention are based on a conductive filler dispersed in a minor phase material, forming a binary composite; the binary composite being mixed with at least one major phase polymeric material. More specifically, the present invention may be achieved by adhering to the hereinafter discussed four general principles and alternate hereinafter described embodiments.
  • the conductive filler content is preferably at or just greater than the percolation threshold in the minor phase material (i.e. the lowest concentration of conductive filler content required to generate a continuous conductive network in the minor phase material); (2) the minor phase content is at or just greater than the percolation threshold in the major phase material (i.e. the lowest concentration of minor phase material required to generate a continuous conductive network in the major phase material); (3) the minor phase material is semicrystalline; and (4) the major/minor phase blend is immiscible having distinct phases.
  • a semiconductive jacket material for jacketing a cable said semiconductive jacket 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 semiconductive jacket material of a ternary composite having distinct co-continuous phases.
  • the material chosen for the conductive filler in any of the embodiments of the present invention influences the amount of conductive filler required to meet or exceed the percolation threshold to form a conductive network.
  • the conductive filler material may be any suitable material exhibiting conductivity and should have a chemical structure which results in an inherently high conductivity and an affinity to develop a strong network.
  • the conductive filler material may, for example, be selected from the group consisting of carbon black (CB), graphite, metallic particles, intrinsically conductive polymers, carbon fibers, and mixtures thereof.
  • the CB may be an "acetylene black" or a "furnace black” or any commercial grade of conductive CB, the acetylene blacks being superior in producing conductive blends.
  • Exemplary CBs are also disclosed in U.S. Patent No. 5,556,697, the contents of which are herein incorporated by reference.
  • "Furnace blacks” are lower quality CBs and are inferior in their ability to produce conductive blends when compared to "acetylene blacks", which are fabricated from the pyrolysis of acetylene. Therefore "acetylene blacks” are most preferred in the present invention over other CB types.
  • Intrinsically conductive polymers such as polyacetylene, polyaniline, polypyrrole, mixtures thereof and the like, are also preferable for optimizing the reduction of conductive filler in the present invention and thus may also be employed as the conductive filler material.
  • An important feature of the present invention is the low amount of conductive filler material employed while still maintaining a desired level of conductivity.
  • the particular weight percent of conductive filler material employed is dependent upon the type of conductive filler material, and the type of minor phase material and major phase material.
  • the conductive filler content can be as high as 10-12 percent by weight of the total composite.
  • the weight percent may be quite high (85% or higher by weight of the total composite), while the volume fraction would be very low ( ⁇ 10%).
  • One skilled in the art would recognize that such values may be determined experimentally for each set of chosen materials. An important criteria, however, is that it is an amount sufficient to meet or exceed the percolation threshold which varies depending upon the selected materials.
  • the minor phase material may be about 44% by weight high density polyethylene (HDPE); the conductive filler may be about ⁇ 6% by weight furnace grade CB; and the major phase material may be about 50% by weight poly(ethylene-co-vinyl-acetate (EVA), the EVA having a vinyl acetate (VA) content of from about 12% to about 45% by weight. If an acetylene black or an intrinsically conductive polymer or carbon fiber is used as the conductive filler in this example, the conductive filler content may be ⁇ 6% and preferably ⁇ about 4% by weight. Based on the foregoing and for example, the minor phase material may be from about 30% to about 50% by weight HDPE and the EVA may be from about 65% to about 50% by weight EVA depending on the VA content in the EVA.
  • HDPE high density polyethylene
  • the conductive filler may be about ⁇ 6% by weight furnace grade CB
  • the major phase material may be about 50% by weight poly(ethylene-co-vinyl-acetate (EVA), the EVA
  • the minor phase material for each embodiment of the present invention must be semicrystalline in nature and the crystallinity may range from about 30% to about 80% and preferably ⁇ about 70% based on the heat of fusion of a perfect crystal.
  • Suitable minor phase materials include any semicrystalline polymer such as HDPE, polypropylene, polypropene, poly-1-butene, poly(styrene) (PS), polycarbonate, poly(ethylene terephthalate), nylon 66, nylon 6 and mixtures thereof.
  • the level of minor phase material content required to meet or exceed the percolation threshold in the major phase material and to meet the required mechanical properties for semiconducting cable jackets is dependent on the constituents of the system, such as the conductive filler material and major phase material(s), and the description and the examples set forth herein should serve as a guide. For example, it has been found that for an HDPE/EVA/CB system with a VA content of 40% that the minor phase HDPE/CB should be about ⁇ 45% and preferably 50% to meet the mechanical properties required in a suitable jacket material, although less is needed to meet the electrical properties.
  • Suitable materials for the major phase material may be any polymeric material which meets the afore-described criteria for not engaging in electrostatic interactions that promote miscibility in relation to the heretofore described suitable minor phase materials. It should be noted that minor electrostatic interactions may be permissible within the above criteria as long as miscibility is not promoted. That is, the blend must be immiscible. Furthermore, the solubility parameter difference ( ⁇ A - ⁇ B ) of the minor and major phase materials in the ternary composites of the present invention meet the following criteria for immiscibility: U L ⁇ ( ⁇ A - ⁇ B ) 2 ⁇ 0 Where,
  • Suitable materials for the major phase material may include, for example, EVA, polybutylene terephthalate, PS, poly(methyl methacrylate) (PMMA), polyethylene, polypropylene, polyisobutylene, poly(vinyl chloride), poly(vinylidene chloride), poly(tetrafluoroethylene), poly(vinyl acetate), poly(methyl acrylate), polyacrylonitrile, polybutadiene, poly(ethylene terephthalate), poly(8-aminocaprylic acid), poly(hexamethylene adipamide) and mixtures thereof.
  • EVA polybutylene terephthalate
  • PS poly(methyl methacrylate)
  • PMMA poly(methyl methacrylate)
  • exemplary major/minor pairs may include the following. That is, minor phase materials polyethylene, polypropene and poly-1-butene may be paired with major phase materials PS, poly(vinyl chloride), poly(vinylidene chloride), poly(tetrafluoroethylene), poly(vinyl acetate), poly(methyl acrylate), poly(methyl methacrylate), polyacrylonitrile, polybutadiene, poly(ethylene terephthalate), poly(8-aminocaprylic acid), poly(hexamethylene adipamide). Similarly, minor phase materials PS, polycarbonate, poly(ethylene terephthalate), nylon 66, nylon 6 may be paired with major phase materials polyethylene, polypropylene and polyisobutylene.
  • Another embodiment of the present invention employs a minor phase material of HDPE with a crystallinity of greater than about 70%, conductive filler of furnace grade CB and a major phase material of EVA. If the VA in the EVA is greater than about 40% by weight, the HDPE/CB minor phase material with a 12% by weight conductive filler content in the minor phase material (which is about 6% by weight of total composite), should be equal to or in excess of about 50% by weight of the total composite to meet both conductivity and mechanical property criteria for semiconductive cable jackets.
  • the level of HDPE/CB minor phase material may be less than about 50% by weight of the total composite provided that the HDPE/CB content is sufficient to exceed the percolation threshold required to generate a continuous conductive network in the EVA.
  • the HDPE/CB content is sufficient to exceed the percolation threshold required to generate a continuous conductive network in the EVA and meet the requirements for a semiconductive cable jacket may be verified experimentally by measuring the volume resistivity of the material. For example, a volume resistivity of ⁇ 100 ⁇ m is required.
  • the semiconductive jacket material further comprises a second major phase material, wherein said ternary composite is dispersed in an amount 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 semiconductive jacket material of a quaternary composite having distinct co-continuous phases.
  • the second major phase material may be selected as described above for the previously discussed major phase material.
  • the amount of ternary composite sufficient for the ternary composite to be continuous within the second major phase material is dependent upon the constituents of the system and may be determined experimentally by measuring the volume resistivity as a function of ternary composite content to ensure that semiconductivity results.
  • a method of producing a semiconductive jacket material for jacketing cables is disclosed.
  • a semicrystalline polymer having a melting temperature is mixed in a mixer, wherein the mixer is preheated to above the melting temperature of the semicrystalline polymer.
  • a conductive filler material is added to the semicrystalline polymer in the mixer in an amount ⁇ an amount required to generate a continuous conductive network in the semicrystalline polymer.
  • the conductive filler material may be added in an amount between about 0.1 weight percent and about 12 weight percent for a HDPE/EVA/CB system.
  • the amount of conductive filler material employed is dependent upon the conductive filler material and the other particular constituents of the system.
  • the conductive filler material and semicrystalline polymer are conventionally mixed for a time and at a speed sufficient to insure a uniform distribution of the conductive filler in the semicrystalline polymer, thereby forming a binary composite.
  • a major phase material having a melting temperature is conventionally mixed with the binary composite in a mixer preheated to above the melting temperature of the major phase material, for a time and at a speed sufficient to insure a uniform distribution of said binary composite in the major phase material.
  • the weight ratio of the binary composite to the major phase material is sufficient for the binary composite to be ⁇ an amount required to generate a continuous conductive network in the major phase material, the major phase material being selected from a group of polymers which when mixed with the binary composite will not engage in electrostatic interactions that promote miscibility, such that a semiconductive jacket material of a ternary composite with distinct co-continuous phases is formed.
  • non-limiting parameters may be particularly employed: from about 0.1% by weight to about 10% by weight conductive filler; from about 49.9% by weight to about 44% by weight HDPE; and about 50% by weight EVA if VA is about 40% by weight.
  • the semicrystalline polymer may be selected from the afore-described minor phase materials and may be present in the amounts described therefor.
  • a second major phase material having a melting temperature is conventionally mixed with the afore-described ternary composite in a mixer preheated to above the melting temperature of the second major phase material, for a time and at a speed sufficient to insure a uniform distribution of said ternary composite in the second major phase material.
  • the weight ratio of the ternary composite to the second major phase material is sufficient for the ternary composite to be ⁇ the percolation threshold required to generate a continuous conductive network in the second major phase material, the second major phase material being selected from a group of polymers which when mixed with the ternary composite will not engage in electrostatic interactions that promote miscibility, such that a semiconductive jacket material of a quaternary composite with distinct co-continuous phases is formed.
  • the second major phase material may be as previously described for the major phase material.
  • the conductive filler content is just above percolation threshold in a minor phase material forming a binary composite.
  • the binary composite is mixed just above the percolation threshold with a major phase material, forming a ternary composite.
  • the ternary composite is mixed with a second major phase material just above the percolation threshold.
  • a quaternary composite results which preferably has less than about 3% by weight conductive filler content with respect to the total quaternary composite weight, yet which forms a continuous conductive network in the composite.
  • a requirement for this embodiment is that the resultant composite is an immiscible blend with distinct phases, and that the conductive filler is in the continuous minor phase.
  • a quaternary composite of the present invention could be formed with a minor phase of "furnace grade" CB in HDPE; the CB comprising about 3.6% by weight of the quaternary composite and about 26.4% by weight HDPE, the major phase material being about 30% by weight EVA and about 40% by weight PS.
  • CB "furnace grade" CB in HDPE
  • the major phase material being about 30% by weight EVA and about 40% by weight PS.
  • semiconductive jacket materials of the invention can be formed with more than two major phase materials.
  • the heretofore described quaternary composite may be mixed in an amount sufficient to exceed the amount required to generate a continuous conductive network with a third major phase material, said third major phase material being such that it will not engage in electrostatic interactions that promote miscibility with the second, first or minor phase materials.
  • the resultant composite is an immiscible blend with distinct phases.
  • semiconductive composite materials may be formed by repeating the heretofore described mixing procedure with any number of further major phase materials which meet the requirements for major phase materials set forth heretofore such that the resultant semiconductive composite material is an immiscible polymer blend having distinct co-continuous phases.
  • the afore-described ternary composite, binary composite and/or quaternary composite may be annealed thereby coarsening the morphology of the respective composite.
  • the percolation threshold of the minor phase in the major phase may be further reduced by preferably annealing the final CPC composite from approximately just above the melting temperature of both the minor phase material and the major phase material. This results in reinforcing the phase separation between the major and minor phase materials by coarsening the morphology of the composite, and thus resulting in the formation of a CPC material with reduced conductive filler content which maintains good conductivity.
  • the percolation threshold of the conductive filler in the minor phase material can be reduced by annealing the minor phase/conductive filler composite before mixing in the major phase material.
  • the annealing will result in the threshold concentration for forming conductive networks in the binary composite to be lower when employing semicrystalline polymers as the minor phase material, such as HDPE or isostatic polypropylene.
  • semicrystalline polymers such as HDPE or isostatic polypropylene.
  • annealing of the foregoing minor phase/conductive filler composite refines and increases the crystalline phase.
  • the afore-described binary composite may be annealed to below the binary composite's melting temperature prior to mixing the afore-described major phase material with the binary composite, wherein the second polymer has a melting temperature less than the binary composite's melting temperature.
  • the major phase material and the binary composite being mixed at a temperature below the melting temperature of the binary composite.
  • a reduction of the percolation threshold of the minor phase material in the major phase material may be achieved by modifying the surface area to volume ratio of the minor phase material, thereby increasing the minor phase's affinity to create a conductive network, before mixing the minor phase with the major phase material.
  • This can be accomplished by pulverizing (i.e. crushing) the binary composite of minor phase material with conductive filler dispersed therein, or more preferably by extruding thread-like structures of binary composite as described below.
  • the pulverized or thread-like structures of binary composite are then mixed with the major phase material below the melting temperature of the minor phase material. It is noted that one skilled in the art would readily know how to pulverize the afore-described material.
  • the afore-described binary composite may be extruded into threadlike structures prior to mixing the major phase material with the binary composite, the major phase material having a melting temperature less than the binary composite's melting temperature, wherein the major phase material and the extruded threadlike structures of the binary composite are mixed at a temperature below the melting temperature of the binary composite.
  • the threadlike structures may be, for example, about 2 mm long and about 0.25 mm in diameter and one skilled in the art would readily understand how to extrude the binary composite.
  • a semiconductive jacket of the invention which may be a thermoplastic compound, is shown on an electrical cable 10 .
  • the electrical cable 10 comprises a central core conductor 12 , an overlaying semiconductive conductor shield 14 , at least one polymeric insulation layer 16 formed over the semiconductive conductor shield, a semiconductive insulation shield 18 formed over the insulation layer 16 , and a metal component 20 which may be embedded in the semiconductive insulation shield 18 as shown, or may overlay the semiconductive insulation shield 18 .
  • a semiconductive jacket 22 is preferably extruded over the semiconductive insulation shield 18 by methods readily known to those skilled in the art.
  • the semiconductive jacket may also be applied over an optical fiber cable as shown in Figure 2 or a hybrid cable.
  • Optical fiber cables and hybrid cables (i.e. cables carrying electrical conductors and optical fiber), are often grounded periodically if they contain metallic elements, especially for lightening protection. Further, some optical fiber cables are installed by blowing them into ducts. Often in this process, depending on the duct material, a static charge builds up on the surface of the cable which opposes the charge on the duct, hindering installation. A semiconductive jacket of the present invention on these cables would advantageously dissipate the static charge and ease installation.
  • the optical fiber cable 30 comprises a metallic central strength member 32 , at least one tube 34 containing optical fibers 36 , and a semiconductive jacket 38 formed around the tubes 34 preferably by extruding the semiconductive jacket 38 by methods readily known to those skilled in the art.
  • a layer of armor, waterblocking material, and additional strength member material may be optionally included in the optical cable 30 .
  • Suitable semiconductive jacket materials of the present invention were made using commercial grades of a random copolymer of EVA, HDPE, and furnace grade CB.
  • the semiconductive jacket material is 6% by weight CB, 44% by weight HDPE, and 50% by weight EVA.
  • the characteristics of the materials used in this example are set forth in Table 1.
  • the EVA was selected to have a high concentration, 45% by weight, of V A in order to reinforce the phase separation between the minor phase material (HDPE/CB) and the major phase (EVA).
  • EVA's with lower weight % VA are less preferable for increased conductivity, but could be substituted without departing from the general principles of the invention.
  • the composite was mixed at 170°C in a Brabender internal mixer with a 300 cm 3 cavity using a 40 rpm mixing rate.
  • the mixing procedure for the semiconductive jacket material of the invention comprises adding the HDPE into the preheated rotating mixer and allowing the polymer to mix for 6 minutes.
  • the CB is added to the mixing HDPE and is allowed to mix for an additional 9 minutes, which insures a uniform distribution of CB within the HDPE.
  • the EVA is added and the mixture allowed to mix for an additional 10 minutes.
  • the semiconductive jacket material, thus formed was then molded at a pressure of about 6 MPa for 12 minutes at 170°C into a plaque of about 0.75 mm in thickness for testing.
  • the electrical conductivity of the resultant composite was measured by cutting 101.6 mm x 6.35 mm x 1.8 mm strips from the molded plaque, and colloidal silver paint was used to fabricate electrodes 50 mm apart along the strips in order to remove the contact resistance.
  • a Fluke 75 Series II digital multimeter and a 2 point technique was used to measure the electrical resistance of the strips.
  • this example demonstrates the ability to make a semiconducting jacket with low conductive filler content that meets, within the margin of error, the "Semiconducting Jacket Type 1".
  • Suitable semiconductive jacket materials of the present invention may be made using commercial grades of a random copolymer of EVA, HDPE, and furnace grade CB.
  • the semiconductive jacket material is 6% by weight CB, 44% by weight HDPE, and 50% by weight EVA.
  • the characteristics of the materials which may be used in this example are set forth in Table 3.
  • the EVA is selected to have a lower concentration, 25% by weight, of VA than that of Example 1. While the higher VA content in Example 1 reinforces the phase separation between the minor phase material (HDPE/CB) and the major phase (EVA), which results in better conductivity of the resultant composite material.
  • EVA's with lower weight % VA will have increased crystallinity which will enhance the mechanical properties of the resultant semiconductive material without a significant loss in conductivity. It is expected that the resistivity of the semiconductive jacket material of this example will be within industry specifications, that is ⁇ 100 ⁇ m with improved tensile strength and elongation properties.
  • the composite is mixed at 170°C in a Brabender internal mixer with a 300 cm 3 cavity using a 40 rpm mixing rate.
  • the mixing procedure for the semiconductive jacket material of the invention comprises adding the HDPE into the preheated rotating mixer and allowing the polymer to mix for 6 minutes.
  • the CB is added to the mixing HDPE and is allowed to mix for an additional 9 minutes, which insures a uniform distribution of CB within the HDPE.
  • the EVA is added and the mixture allowed to mix for an additional 10 minutes.
  • the semiconductive jacket material, thus formed is then molded at a pressure of about 6 MPa for 12 minutes at 170°C into a plaque of about 0.75 mm in thickness.
  • a quaternary immiscible blend may be formed using the constituents: PS, EVA, HDPE, and CB by the method comprising the steps set forth hereinafter.
  • the PS is added to the Brabender internal rotating mixer preheated to 170°C and allowed to mix for about 6 minutes at 40 rpm, prior to the addition of the EVA/HDPE/CB ternary composite already prepared as, for instance, set forth in the foregoing examples. This blend is allowed to mix for an additional 9 minutes.
  • the final quaternary composite is then molded at a pressure of about 6 MPa for 12 minutes at 170°C in plaques of about 0.75 mm in thickness.
  • the follow constituents may be employed: 3.6% by weight CB; 26.4% by weight HDPE; 30% by weight EVA; 40% by weight PS; and 40% by weight VA in the EVA.
  • the quaternary composite is an immiscible blend with distinct phases, and that the conductive filler is in the continuous phases.
  • a CPC composite with less than about 4% by weight of CB of the total PS/EVA/HDPE/CB may be formed.
  • a CPC material having less than or equal to about 6% by weight conductive dispersion content of CB residing in a minor phase of HDPE is mixed with EVA.
  • EVA electronic vapor deposition
  • a highly conductive compound may be generated with a resistivity of less than about 100 ⁇ m.
  • the rheology of the compound is more analogous to an unfilled compound in terms of extrusion properties and processability.
  • the CPC can be further tailored to meet the mechanical properties required for semiconductive cable jackets by modifying the level of VA in the EVA in further accordance with the present invention, as demonstrated in Example 2.
  • the afore-described advantages and superior results may be achieved by the selection of a conductive filler with a chemical structure which results in an inherently high conductivity and an affinity to develop a strong network, such as CB, and by the modification of the thermodynamic stability of the conductive filler and the minor polymer phases to encourage coarsening of the filler/minor phase morphology, such as by the afore-described annealing technique.
  • the advantages are also realized by selecting a minor phase polymer with a high level of crystallinity such that the conductive filler and minor phase material preferentially phase separate in order to increase the concentration of the conductive filler in the amorphous phase, as well as by reducing the percolation threshold of the minor phase/conductive filler material in the major phase material through a processing approach, such as the afore-described extruding, annealing and pulverizing means, to changing the morphology of the minor phase/conductive filler material.
  • advantages of the present invention are achieved by post-annealing of the CPC material to coarsen the morphology of the major/minor phase, as well as by increasing the crystalline component of the major phase polymer; for example, modifying the VA content in the EVA as heretofore described or by incorporating 0.01% by weight to about 2% by weight of a nucleating agent in the major phase material to promote crystallinity; in order to increase the concentration of the minor phase in the amorphous major phase.
  • nucleating agents and antioxidants may be added into the composite material or in the major phase of minor phase materials in the amount of about 0.01% by weight to about 5% by weight without departing from the spirit and scope of the invention.
  • exemplary nucleating agents are talc, silica, mica, and kaolin.
  • antioxidants are: hindered phenols such as tetrakis[methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]-methane, bis[(beta-(3,5-diter-butyl-4-hydroxybenzyl)methylcarboxyethyl)]sulphide, 4,4-thiobis(2-methyl-6-tert-butylphenol), 4,4-thiobis(2-tert-butyl-5-methylphenol), 2,2-thiobis(4-methyl-6-tert-butylphenol), and thiodethylene bis(3,5-di-tert-butyl-4-hydroxy)hydrocinnamate; phosphites and phosphonites such as tris(2,4-di-tert-butylphenyl)phosphite and di-tert-butylphenylphosphonitie; thio compounds such as dilaurylthiodipropionte, dimyr

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Conductive Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Insulated Conductors (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Inorganic Insulating Materials (AREA)
EP99305465A 1998-07-10 1999-07-09 Halbleitermaterial, Verfahren zur Herstellung desselben und damit ummanteltes Kabel Expired - Lifetime EP0971368B1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US09/113,914 US6514608B1 (en) 1998-07-10 1998-07-10 Semiconductive jacket for cable and cable jacketed therewith
US113914 1998-07-10
US09/306,735 US6506492B1 (en) 1998-07-10 1999-05-07 Semiconductive jacket for cable and cable jacketed therewith
US307735 1999-05-07
US09/307,735 US6189211B1 (en) 1998-05-15 1999-05-10 Method and arrangement for carrying out repair and/or maintenance work in the inner casing of a multishell turbomachine

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EP0971368A1 true EP0971368A1 (de) 2000-01-12
EP0971368B1 EP0971368B1 (de) 2004-11-17

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AT (1) ATE282888T1 (de)
AU (1) AU767532B2 (de)
BR (1) BR9902675B1 (de)
CA (1) CA2277704C (de)
DE (1) DE69921904T2 (de)
ES (1) ES2234211T3 (de)
NZ (1) NZ336672A (de)

Cited By (6)

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Publication number Priority date Publication date Assignee Title
WO2000068299A2 (en) * 1999-05-07 2000-11-16 General Electric Company Conductive compositions with compositionally controlled bulk resistivity
US6221283B1 (en) 1999-05-07 2001-04-24 General Electric Company Conductive compositions with compositionally controlled bulk resistivity
EP1150313A2 (de) * 2000-04-25 2001-10-31 Abb Research Ltd. Hochspannungsisolationssystem
US6331586B1 (en) 1998-02-12 2001-12-18 Cabot Corporation Conductive polymer blends with finely divided conductive material selectively localized in continuous polymer phase or continuous interface
WO2011154287A1 (en) 2010-06-10 2011-12-15 Borealis Ag New composition and use thereof
AU2007272311B2 (en) * 2006-07-13 2014-02-06 Commonwealth Scientific And Industrial Research Organisation Electrical conductive element

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US4265789A (en) * 1979-10-22 1981-05-05 Polymer Cencentrates, Inc. Conductive polymer processable as a thermoplastic
EP0337487A1 (de) * 1988-04-15 1989-10-18 Showa Denko Kabushiki Kaisha Elektroleitfähige Polymerzusammensetzung
US5037999A (en) * 1990-03-08 1991-08-06 W. L. Gore & Associates Conductively-jacketed coaxial cable
EP0524700A1 (de) * 1987-03-11 1993-01-27 Raychem Corporation Polymermischungen
WO1998003578A1 (en) * 1996-07-24 1998-01-29 The Dow Chemical Company Thermoplastic polymer compositions with modified electrical conductivity

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US6277303B1 (en) * 1998-07-10 2001-08-21 Pirelli Cable Corporation Conductive polymer composite materials and methods of making same

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US4265789A (en) * 1979-10-22 1981-05-05 Polymer Cencentrates, Inc. Conductive polymer processable as a thermoplastic
EP0524700A1 (de) * 1987-03-11 1993-01-27 Raychem Corporation Polymermischungen
EP0337487A1 (de) * 1988-04-15 1989-10-18 Showa Denko Kabushiki Kaisha Elektroleitfähige Polymerzusammensetzung
US5037999A (en) * 1990-03-08 1991-08-06 W. L. Gore & Associates Conductively-jacketed coaxial cable
WO1998003578A1 (en) * 1996-07-24 1998-01-29 The Dow Chemical Company Thermoplastic polymer compositions with modified electrical conductivity

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6331586B1 (en) 1998-02-12 2001-12-18 Cabot Corporation Conductive polymer blends with finely divided conductive material selectively localized in continuous polymer phase or continuous interface
WO2000068299A2 (en) * 1999-05-07 2000-11-16 General Electric Company Conductive compositions with compositionally controlled bulk resistivity
WO2000068299A3 (en) * 1999-05-07 2001-01-18 Gen Electric Conductive compositions with compositionally controlled bulk resistivity
US6221283B1 (en) 1999-05-07 2001-04-24 General Electric Company Conductive compositions with compositionally controlled bulk resistivity
EP1150313A2 (de) * 2000-04-25 2001-10-31 Abb Research Ltd. Hochspannungsisolationssystem
EP1150313A3 (de) * 2000-04-25 2002-05-29 Abb Research Ltd. Hochspannungsisolationssystem
US6791033B2 (en) 2000-04-25 2004-09-14 Abb Research Ltd. High-voltage insulation system
AU2007272311B2 (en) * 2006-07-13 2014-02-06 Commonwealth Scientific And Industrial Research Organisation Electrical conductive element
WO2011154287A1 (en) 2010-06-10 2011-12-15 Borealis Ag New composition and use thereof

Also Published As

Publication number Publication date
CA2277704A1 (en) 2000-01-10
EP0971368B1 (de) 2004-11-17
BR9902675B1 (pt) 2011-11-01
AU767532B2 (en) 2003-11-13
ATE282888T1 (de) 2004-12-15
BR9902675A (pt) 2001-03-20
DE69921904D1 (de) 2004-12-23
NZ336672A (en) 1999-11-29
AU3913899A (en) 2000-02-03
DE69921904T2 (de) 2006-03-02
ES2234211T3 (es) 2005-06-16
CA2277704C (en) 2009-03-17

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