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EP2224459B1 - High voltage electrical cable - Google Patents

High voltage electrical cable Download PDF

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Publication number
EP2224459B1
EP2224459B1 EP10154403.9A EP10154403A EP2224459B1 EP 2224459 B1 EP2224459 B1 EP 2224459B1 EP 10154403 A EP10154403 A EP 10154403A EP 2224459 B1 EP2224459 B1 EP 2224459B1
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EP
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Prior art keywords
weight
composition
polymer
parts
cable according
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EP10154403.9A
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German (de)
French (fr)
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EP2224459A1 (en
Inventor
Christian Koelblin
Daniel Milan
Christophe Mercado
Frédéric Bechard
Franz Daenekas
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Nexans SA
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Nexans SA
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B9/00—Power cables
    • H01B9/02—Power cables with screens or conductive layers, e.g. for avoiding large potential gradients
    • H01B9/027—Power cables with screens or conductive layers, e.g. for avoiding large potential gradients composed of semi-conducting layers

Definitions

  • the present invention relates to an electrical cable comprising a conductive element, and successively around this conductive element, an electrically insulating layer, a metal screen and an outer protective sheath.
  • the high or very high voltage power cables typically comprise a central conductive element and, successively and coaxially around this conductive element, an internal semiconductor screen, an extruded electrically insulating layer, an external semiconductor screen, a metal screen and an outer protective sheath.
  • the outer protective sheath is in particular increasingly made of materials retarding the propagation of the flame or resistant to the propagation of the flame.
  • a first technique consists in coating the outer protective sheath of the electrical cable with a layer of graphite in powder form.
  • the handling of the graphite powder is delicate and involves a risk of fouling in the sheathing shops.
  • This non-homogeneity of the graphite layer on the outer protective sheath does not make it possible to perform said electrical test reliably.
  • a second technique consists in applying a conductive varnish to the outer protective sheath of the electric cable.
  • the disadvantage of this technique is the presence of volatile solvents in the conductive lacquer which may be irritating and / or toxic.
  • said varnish has mechanical properties very different from those of the outer protective sheath, which can compromise the good adhesion of the varnish on the outer protective sheath during handling of the electric cable.
  • the object of the present invention is to overcome the disadvantages of the techniques of the prior art.
  • the present invention relates to an electrical cable comprising a conductive element, and successively around this conductive element, an electrically insulating layer, a metal screen and an outer protective sheath, characterized in that further comprises an extruded outer layer surrounding the outer protective sheath, said extruded outer layer being directly in contact with said outer protective sheath, and being obtained from a composition comprising more than 50.0 parts by weight of apolar polymer per 100 parts by weight of polymer in the composition and an electrically conductive filler.
  • This outer layer is also called (electrically) "conductive" layer.
  • conductor or “conductor” used in the present invention should also be understood to mean “semiconductor” or “semiconductor”.
  • the electrical cable of the invention advantageously has an extruded outer layer deposited homogeneously directly on the outer protective sheath with a substantially identical contact surface on the entire outer protective sheath.
  • the assembly formed by the outer protective sheath and the extruded outer layer can therefore be considered as a bilayer, said bilayer preferably having no intermediate layer interposed between the outer protective sheath and the outer layer.
  • the extruded outer layer has significantly improved adhesion. Thus, it can not be detached from the outer protective sheath when handling or installing the electric cable.
  • the electrical test can be easily applied to the electrical cable of the invention and give reliable results on the quality of protection of the outer protective sheath.
  • the extruded outer layer offers optimized mechanical properties (eg tensile strength, elongation at break and modulus of elasticity), and in particular improved flexibility (ie modulus of elasticity) which advantageously reduces the risk of cracking. of said outer layer during, for example, the handling and / or installation of the cable.
  • the composition may comprise at least 60 parts by weight of apolar polymer per 100 parts by weight of polymer in the composition, and preferably at least 80 parts by weight of apolar polymer per 100 parts by weight of polymer in the composition.
  • it may also comprise an apolar polymer (or a mixture of apolar polymer) as sole polymer in the composition.
  • polymer as such generally means homopolymer or copolymer, the polymer being a thermoplastic or elastomeric polymer. It is preferred to use the thermoplastic polymers and the composition will be called in this case a thermoplastic composition.
  • the apolar polymer is a polyolefin, comprising homopolymers and copolymers of olefins, preferably of the low-density type.
  • the low density polyolefins typically have a density of at most 0.930 g / cm 3 , preferably at most 0.920 g / cm 3 .
  • the density of the polyolefins of the invention is conventionally determined by methods well known in the prior art detailed in standards ASTM D1505 or ISO 1183.
  • the low density polyolefin may be chosen from linear low density polyethylenes (LLDPE), polyethylenes very low density (VLDPE), and ultra low density polyethylenes (ULDPE), or a mixture thereof.
  • apolar polymers of the invention thus do not substantially comprise polar groups such as, for example, acrylate, carboxylic or vinyl acetate groups.
  • the melting temperature of the apolar polymer may be at least 110 ° C, preferably at least 120 ° C.
  • the melting temperature of the polymers of the present invention is conventionally measured at the melting peak of said polymer by differential scanning calorimetry (DSC) with a temperature ramp of 10 ° C./min under a nitrogen atmosphere.
  • the melt index (MFR) (according to ASTM D 1238 or ISO 1133) of the apolar polymer may be at most 30 g / 10 min (190 ° C., 2.16 kg). ), preferably at most 20g / 10min, and particularly preferably at most 10g / 10min.
  • the apolar polymer may be derived from a polymerization in the presence of a conventional Ziegler-Natta or Philips catalyst.
  • a Ziegler-Natta LLDPE is used.
  • Ziegler-Natta LLDPE known as C4-LLDPE or copolymer of ethylene and butene, is used.
  • the composition further comprises a polar polymer, preferably at most 40 parts by weight of polar polymer per 100 parts by weight of polymer in the composition, and particularly preferably at most 20 parts by weight of polar polymer per 100 parts by weight of polymer in the composition.
  • a polar polymer in the composition makes it possible to improve the dispersion of the electrically conductive fillers in the composition and the adhesion of the extruded outer layer to the outer protective sheath as a function of the polar or apolar nature of said outer sheath.
  • the polar polymer may be a copolymer of ethylene acrylate, preferably chosen from ethylene butyl acrylate copolymers (EBA), ethylene ethyl acrylate copolymers (EEA), and ethylene copolymers. methyl acrylates (EMA), or a mixture thereof.
  • EBA ethylene butyl acrylate copolymers
  • EAA ethylene ethyl acrylate copolymers
  • EMA methyl acrylates
  • composition of the invention may comprise between 30 and 90% by weight of polymer.
  • the composition may comprise at least 10% by weight of electrically conductive filler, preferably at most 40% by weight of electrically conductive filler, and particularly preferably preferred between 15 and 30% by weight of electrically conductive filler.
  • the volume conductivity of the composition may be insufficient.
  • the preparation and the implementation of the composition can become difficult, and the composition also becomes economically unfavorable.
  • the electrically conductive filler may be selected from carbon black, graphite, carbon nanotubes, doped inorganic fillers such as, for example, aluminum-doped zinc oxide having a high and linear conductivity, and powders. intrinsic conductive polymers, or a mixture thereof.
  • the preferred electrically conductive filler of the invention is carbon black.
  • composition according to the invention may further comprise other fillers, additives, adjuvants, stabilizers, and / or anti-aging agents.
  • the stabilizers may typically be antioxidants, these antioxidants being preferably selected from sterically hindered phenolic antioxidants such as, for example, tetrakismethylene (3,5-di-t-butyl-4-hydroxy-hydrocinnamate) methane, 2,2 ' -thiodiethylene bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2'-Thiobis (6-t-butyl-4-methylphenol) or 2,2'-methylenebis (6-t-butyl-4-methylphenol); and phosphorus-based antioxidants such as, for example, Tris (2,4-di-t-butylphenyl) phosphite.
  • sterically hindered phenolic antioxidants such as, for example, tetrakismethylene (3,5-di-t-butyl-4-hydroxy-hydrocinnamate) methane, 2,2 ' -thiodiethylene bis [
  • the type of stabilizer and its level in the composition will be chosen according to the maximum temperature experienced by the polymer during the production of the mixture and during the extrusion operation on the cable as well as according to the maximum duration of exposure to this temperature. .
  • the anti-aging agents may typically be thermal aging protection agents such as quinolines, for example poly-2,2,4-trimethyl-1,2-dihydroquinoline (TMQ).
  • thermal aging protection agents such as quinolines, for example poly-2,2,4-trimethyl-1,2-dihydroquinoline (TMQ).
  • Stabilizers and / or anti-aging agents may be added to the composition of the invention in an amount of at most 2% by weight, preferably 0.2 to 1% by weight.
  • the other fillers may be halogen-free inorganic fillers intended to improve the fire behavior of the composition, such as, for example, clear fillers, and more particularly flame retardant fillers known as "HFFR" fillers for the " Halogen Free Flame Retardant " anglicism, such as aluminum trihydrate (ATH), magnesium dihydrate (MDH), antimony trioxide or zinc borate.
  • Said clear charges may further comprise a surface treatment, for example to facilitate their incorporation into the polymer melt during the mixing of the composition or to increase their effectiveness against the effects of fire.
  • the composition according to the invention can thus advantageously also comprise a flame-retardant filler.
  • the other charges may also be charges capable of reducing the phenomenon of incandescent drops during a fire (" anti-drip-agent "), preferably without halogen.
  • the other fillers taken independently of one another or in combination, can be added to the composition of the invention in an amount of at most 50% by weight, and preferably in an amount of at most 30% by weight. .
  • the composition may comprise at least 10% by weight of said other fillers.
  • the outer layer may be crosslinked or not.
  • the outer layer of the invention preferably has a thickness of at most 400 ⁇ m, and preferably at most 300 ⁇ m. This thickness is related to an outer layer called " skin " type.
  • the outer protective sheath of the cable according to the invention preferably has a Shore D hardness of at least 50 according to ISO 868.
  • the adhesion of the outer layer may be improved by the nature of the outer protective sheath, especially when said outer sheath is apolar type, and optionally loaded with mineral fillers, including flame retardant fillers.
  • the various polymeric layers of the electrical cable of the invention preferably do not include halogenated compounds.
  • halogenated compounds may be of any kind, such as, for example, fluorinated polymers or chlorinated polymers such as polyvinyl chloride (PVC), halogenated plasticizers, halogenated mineral fillers, etc.
  • the latter further comprises a semiconductor screen internal between the conductive element and the electrically insulating layer, and an external semiconductor screen between the electrically insulating layer and the metal screen.
  • the electric cable thus formed is called a high or very high voltage power cable.
  • the metal screen can be brought into contact with the high voltage source for example by cutting a "window" in the outer protective sheath to place an electrode in the metal screen.
  • the voltage is increased to a predetermined value, and left active for a predetermined time.
  • the predetermined value of the voltage is set at 20 kV and that of the duration is fixed at 15 minutes.
  • the outer protective sheath When a drop in the value of the voltage is observed as well as an increase and / or an instability of the charged charging current, the outer protective sheath has a defect.
  • the fall of the value of the voltage on the one hand, and the increase and / or the instability of the charge current on the other hand, are easily identifiable respectively using a high voltage voltmeter in combination with a voltage reducer (for voltage) and an ohmic shunt in combination with a suitable voltmeter (for current).
  • the defect can then be located for example by electrical echometry, then the damaged part of the cable can be repaired.
  • the figure 1 illustrates a schematic perspective exploded view of an electric cable according to a preferred embodiment of the invention.
  • the power cable 1 at high voltage or at very high voltage, represented on the figure 1 comprises a central conducting element 2, in particular made of copper or aluminum, and, successively and coaxially around this element, a so-called “internal” semiconductor layer 3, an electrically insulating layer 4, a semiconductor layer 5 called “ external ", a metal screen 6 of grounding and / or protection, an outer sheath 7 of protection, and an outer layer 8 extruded according to the invention.
  • Layers 3, 4 and 5 are conventionally extruded and crosslinked layers by methods well known to those skilled in the art.
  • the presence of the semiconductor layers 3 and 5 is preferred, but not essential.
  • the protective structure which includes the metal screen 6 and the outer sheath 7 protection, may also include other protective elements.
  • the protective structure of this cable is as such of known type and outside the scope of the present invention.
  • compositions 1 to 5 are mixed in a continuous mixer or a twin-screw extruder.
  • the polymer, and optionally the additives, are introduced by appropriate metering means into the mixer, the polymer being melt.
  • the electrically conductive charges, and possibly the other charges are introduced into the melt and homogenized.
  • the mixture obtained is granulated using a granulation device.
  • the granules obtained in the granulation step are extruded, the extrudate being deposited around an outer protective sheath (also extruded) with a thickness of 2 to 3 mm surrounding a wire of a section of 1.5 mm 2 .
  • the respective thickness of the outer layers, obtained respectively from compositions 1 to 3 extruded, is between 0.15 and 0.2 mm.
  • the bilayers of the electric cables thus obtained are subjected to a visual inspection.
  • the HFFR sheath (or outer protective sheath) of Table 1 is an HFFR material marketed by NEXANS under the reference HS3411-T.
  • thermoplastic compositions of the invention can be extruded on the outer protective sheath of the cable without significant detachment of the outer layer can be found, unlike compositions 1 and 2.
  • Composition 2 Composition 3
  • Composition 4 Composition 5 Resistance to fracture (MPa) 11.7 29.8 24.2 16.5 15.5 Elongation at break (%) 450 513 575 518 454
  • Modulus of elasticity (MPa) NM * 1620 1046 1056 1267 Volume resistivity at 23 ° C (Ohm.m) 0.25 10 0.22 0.36 0.25 Hardness (Shore D) 55 NM * 57 NM * NM * Burn time in vertical direction of solid rods (seconds) NM * NM * 259 298 366 Evaluation of the firing during the test of burning of solid rods NM * NM * Easy firing Medium firing Difficult firing * NM Value or characteristic not measured
  • the mechanical properties (tensile strength, elongation at break and modulus of elasticity) as well as the volume resistivity at 23 ° C were measured on specimens taken from extruded strips (0.3 mm thick) obtained from compositions 1 to 5.
  • the breaking strength and elongation at break are determined according to IEC 60811-1-1 standard, the specimens being of the type “dumbbells" ISO 37-2 and the tensile speed used being 100 mm / min.
  • the modulus of elasticity (or Young's modulus) is determined by tensile tests according to ISO 527-1 or ASTM D 638, the specimens being of the type “dumbbells" ISO 37-2 and the traction speed used being 100 mm / min.
  • the modulus of elasticity makes it possible to characterize the rigidity of a material. The higher its value, the more the material is said to be rigid.
  • the volume resistivity is determined according to the ASTM D991 standard or a method derived from the ISO 3915 standard.
  • the Shore D value is determined using a durometer, according to ISO868 or ASTM D 2240.
  • the burning time in the vertical direction of a flame of solid rods is determined as follows. Solid rods with a diameter of 4 mm are extruded with each of compositions 1 to 5. These rods are then dried for 48 hours at a temperature of 70 ° C. in a hot air oven to eliminate any influence of absorbed moisture. on fire behavior. After drying, the rushes are cut into pieces with a length of 22 cm. Under a fume hood is placed a laboratory stand on which is fixed a clamping nut at a height of 30 cm. This clamping nut holds a short stand rod in the horizontal direction. At the end of this rod, a second clamping nut is fixed. Each ring is fixed vertically in this second clamping nut, the clamping length being 2 cm.
  • the free length available for the flame is thus 20 cm.
  • the ring is then fired with a butane flame.
  • the time between the firing of the rod (that is to say when the rod burns all alone) and the complete extinction of the flame, is measured using a stopwatch.
  • 3 rods are burned and the average value of the combustion times thus obtained calculated (in seconds). The interpretation of the values is as such: the longer the burning time, and this only for a combustion on the entire length and where the rod is consumed in total over 20 cm, the fire retardant filler is effective to delay combustion.
  • compositions 3 to 5 show that the compositions according to the invention are much more mechanically flexible, even for compositions 4 and 5 which are heavily loaded. This increased flexibility reduces the risk of cracking of the outer layer during handling and / or installation of the cable.
  • compositions 4 and 5 additionally containing a flame retardant filler of the HFFR type show an increased flame retardancy effect with respect to composition 3, which is particularly pronounced for composition 5.
  • the fire behavior of the assembly consisting of said conductive outer layer according to the invention and the outer protective sheath type HFFR, is very favorable, said assembly also having very good mechanical properties, good electrical conductivity as well as a good membership.

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Description

La présente invention se rapporte à un câble électrique comprenant un élément conducteur, et successivement autour de cet élément conducteur, une couche électriquement isolante, un écran métallique et une gaine extérieure de protectionThe present invention relates to an electrical cable comprising a conductive element, and successively around this conductive element, an electrically insulating layer, a metal screen and an outer protective sheath.

Elle s'applique typiquement, mais non exclusivement, aux domaines des câbles d'énergie à haute ou à très haute tension à courant continu ou alternatif. Ces câbles d'énergie sont typiquement des câbles de 60 à 600 kV.It applies typically, but not exclusively, to the fields of high or very high voltage direct or alternating current power cables. These power cables are typically 60 to 600 kV cables.

Les câbles d'énergie à haute ou à très haute tension comprennent typiquement un élément conducteur central et, successivement et coaxialement autour de cet élément conducteur, un écran semi-conducteur interne, une couche électriquement isolante extrudée, un écran semi-conducteur externe, un écran métallique et une gaine extérieure de protection. La gaine extérieure de protection est notamment réalisée de plus en plus souvent en matières retardant la propagation de la flamme ou résistant à la propagation de la flamme. On parle de gainage de type HFFR (pour l'anglicisme « Halogen Free Flame Retardant »).The high or very high voltage power cables typically comprise a central conductive element and, successively and coaxially around this conductive element, an internal semiconductor screen, an extruded electrically insulating layer, an external semiconductor screen, a metal screen and an outer protective sheath. The outer protective sheath is in particular increasingly made of materials retarding the propagation of the flame or resistant to the propagation of the flame. We speak of cladding type HFFR (for Anglicism " Halogen Free Flame Retardant" ).

On a observé que lors de l'installation de ces câbles électriques, plus particulièrement lors de la pose de ces câbles ou de la pose des jonctions et terminaisons sur ces câbles, la gaine extérieure de protection pouvait être endommagée, et ainsi créer un défaut prématuré dans ladite gaine extérieure qui entraînerait la détérioration du câble notamment par la pénétration d'humidité dans ledit câble.It has been observed that during the installation of these electric cables, especially when laying these cables or laying joints and terminations on these cables, the outer protective sheath could be damaged, and thus create a premature defect in said outer sheath which would cause the deterioration of the cable including the penetration of moisture in said cable.

Afin de vérifier si le câble électrique a été endommagé lors de son installation, il est connu de réaliser un test électrique, utilisant une haute tension à polarité constante (courant continu), entre l'écran métallique et un revêtement conducteur déposé sur ladite gaine extérieure de protection. Ce test peut également être répété tout le long de la vie du câble électrique.In order to verify whether the electrical cable was damaged during its installation, it is known to perform an electrical test, using a high voltage constant polarity (direct current), between the metal screen and a conductive coating deposited on said sheath external protection. This test can also be repeated throughout the life of the power cable.

Une première technique consiste à enduire la gaine extérieure de protection du câble électrique d'une couche de graphite sous forme de poudre. Cependant, la manipulation de la poudre de graphite est délicate et entraîne un risque de salissure dans les ateliers de gainage. En outre, il est difficile de répartir de façon homogène la poudre de graphite sur tout le pourtour de la gaine extérieure de protection du câble électrique par manque d'une forte adhésion de la poudre de graphite sur ladite gaine extérieure. Cette non-homogénéité de la couche de graphite sur la gaine extérieure de protection ne permet pas de réaliser ledit test électrique de façon fiable.A first technique consists in coating the outer protective sheath of the electrical cable with a layer of graphite in powder form. However, the handling of the graphite powder is delicate and involves a risk of fouling in the sheathing shops. In addition, it is difficult to evenly distribute the graphite powder all around the outer sheath of protection of the electric cable for lack of strong adhesion of the graphite powder on said outer sheath. This non-homogeneity of the graphite layer on the outer protective sheath does not make it possible to perform said electrical test reliably.

Une deuxième technique consiste à appliquer un vernis conducteur sur la gaine extérieure de protection du câble électrique. Le désavantage de cette technique est la présence de solvants volatils dans le vernis conducteur qui peuvent être irritants et/ou toxiques. En outre, ledit vernis possède des propriétés mécaniques très différentes de celles de la gaine extérieure de protection, ce qui peut compromettre la bonne adhésion du vernis sur la gaine extérieure de protection lors de la manipulation du câble électrique.A second technique consists in applying a conductive varnish to the outer protective sheath of the electric cable. The disadvantage of this technique is the presence of volatile solvents in the conductive lacquer which may be irritating and / or toxic. In addition, said varnish has mechanical properties very different from those of the outer protective sheath, which can compromise the good adhesion of the varnish on the outer protective sheath during handling of the electric cable.

On connaît en outre le document de Southwire intitulé « High Voltage Solutions» (XP-002541323 ), qui décrit une couche externe semi-conductrice de polyéthylène co-extrudée avec une gaine externe.In addition, the document of Southwire titled "High Voltage Solutions" (XP-002541323 ), which describes a semiconducting outer layer of polyethylene coextruded with an outer sheath.

Le but de la présente invention est de pallier les inconvénients des techniques de l'art antérieur.The object of the present invention is to overcome the disadvantages of the techniques of the prior art.

La présente invention a pour objet un câble électrique comprenant un élément conducteur, et successivement autour de cet élément conducteur, une couche électriquement isolante, un écran métallique et une gaine extérieure de protection, caractérisé en ce qu'il comprend en outre une couche externe extrudée entourant la gaine extérieure de protection, ladite couche externe extrudée étant directement en contact avec ladite gaine extérieure de protection, et étant obtenue à partir d'une composition comprenant plus de 50,0 parties en poids de polymère apolaire pour 100 parties en poids de polymère dans la composition et une charge électriquement conductrice. Cette couche externe est d'ailleurs dite couche (électriquement) « conductrice ».The present invention relates to an electrical cable comprising a conductive element, and successively around this conductive element, an electrically insulating layer, a metal screen and an outer protective sheath, characterized in that further comprises an extruded outer layer surrounding the outer protective sheath, said extruded outer layer being directly in contact with said outer protective sheath, and being obtained from a composition comprising more than 50.0 parts by weight of apolar polymer per 100 parts by weight of polymer in the composition and an electrically conductive filler. This outer layer is also called (electrically) "conductive" layer.

Le terme « conducteur » ou « conductrice » utilisé dans la présente invention doit être également compris comme signifiant « semi-conducteur » ou « semi-conductrice ».The term "conductor" or "conductor" used in the present invention should also be understood to mean "semiconductor" or "semiconductor".

Le câble électrique de l'invention présente avantageusement une couche externe extrudée déposée de façon homogène directement sur la gaine extérieure de protection avec une surface de contact sensiblement identique sur toute la gaine extérieure de protection. L'ensemble formé par la gaine extérieure de protection et la couche externe extrudée peut donc être considéré comme un bicouche, ledit bicouche ne comportant préférentiellement pas de couche intermédiaire intercalée entre la gaine extérieure de protection et la couche externe.The electrical cable of the invention advantageously has an extruded outer layer deposited homogeneously directly on the outer protective sheath with a substantially identical contact surface on the entire outer protective sheath. The assembly formed by the outer protective sheath and the extruded outer layer can therefore be considered as a bilayer, said bilayer preferably having no intermediate layer interposed between the outer protective sheath and the outer layer.

De plus, la couche externe extrudée présente une adhésion améliorée de façon significative. Ainsi, elle ne peut être désolidarisée de la gaine extérieure de protection lors de la manipulation ou de l'installation du câble électrique.In addition, the extruded outer layer has significantly improved adhesion. Thus, it can not be detached from the outer protective sheath when handling or installing the electric cable.

Par conséquent, le test électrique peut être facilement appliqué au câble électrique de l'invention et donner des résultats fiables sur la qualité de la protection de la gaine extérieure de protection.Therefore, the electrical test can be easily applied to the electrical cable of the invention and give reliable results on the quality of protection of the outer protective sheath.

Enfin, la couche externe extrudée offre des propriétés mécaniques optimisées (e.g. résistance à la rupture, allongement à la rupture et module d'élasticité), et notamment une flexibilité (i.e. module d'élasticité) améliorée qui permet de réduire avantageusement le risque de fissuration de ladite couche externe lors, par exemple, de la manipulation et/ou de l'installation du câble.Finally, the extruded outer layer offers optimized mechanical properties (eg tensile strength, elongation at break and modulus of elasticity), and in particular improved flexibility (ie modulus of elasticity) which advantageously reduces the risk of cracking. of said outer layer during, for example, the handling and / or installation of the cable.

De préférence, la composition peut comprendre au moins 60 parties en poids de polymère apolaire pour 100 parties en poids de polymère dans la composition, et de préférence au moins 80 parties en poids de polymère apolaire pour 100 parties en poids de polymère dans la composition. Dans un mode de réalisation particulier, elle peut également comprendre un polymère apolaire (ou un mélange de polymère apolaire) en tant qu'unique polymère dans la composition.Preferably, the composition may comprise at least 60 parts by weight of apolar polymer per 100 parts by weight of polymer in the composition, and preferably at least 80 parts by weight of apolar polymer per 100 parts by weight of polymer in the composition. In a particular embodiment, it may also comprise an apolar polymer (or a mixture of apolar polymer) as sole polymer in the composition.

Le terme « polymère » en tant que tel signifie de façon générale homopolymère ou copolymère, le polymère pouvant être un polymère thermoplastique ou élastomère. On préféra utiliser les polymères thermoplastiques et la composition sera dite dans ce cas composition thermoplastique.The term "polymer" as such generally means homopolymer or copolymer, the polymer being a thermoplastic or elastomeric polymer. It is preferred to use the thermoplastic polymers and the composition will be called in this case a thermoplastic composition.

A titre d'exemple, le polymère apolaire est une polyoléfine, comprenant les homopolymères et les copolymères d'oléfines, de préférence de type basse densité. Les polyoléfines basse densité ont typiquement une densité d'au plus 0,930 g/cm3, de préférence d'au plus 0,920 g/cm3. La densité des polyoléfines de l'invention est classiquement déterminée par des méthodes bien connues de l'art antérieur détaillées dans les normes ASTM D1505 ou ISO 1183. La polyoléfine basse densité peut être choisie parmi les polyéthylènes linéaires basse densité (LLDPE), les polyéthylènes très basse densité (VLDPE), et les polyéthylènes ultra basse densité (ULDPE), ou un de leurs mélanges.By way of example, the apolar polymer is a polyolefin, comprising homopolymers and copolymers of olefins, preferably of the low-density type. The low density polyolefins typically have a density of at most 0.930 g / cm 3 , preferably at most 0.920 g / cm 3 . The density of the polyolefins of the invention is conventionally determined by methods well known in the prior art detailed in standards ASTM D1505 or ISO 1183. The low density polyolefin may be chosen from linear low density polyethylenes (LLDPE), polyethylenes very low density (VLDPE), and ultra low density polyethylenes (ULDPE), or a mixture thereof.

Les polymères apolaires de l'invention ne comportent ainsi sensiblement pas de groupements polaires tels que par exemple des groupements acrylate, carboxylique ou vinyle acétate.The apolar polymers of the invention thus do not substantially comprise polar groups such as, for example, acrylate, carboxylic or vinyl acetate groups.

Selon une caractéristique de l'invention, la température de fusion du polymère apolaire peut être d'au moins 110°C, de préférence d'au moins 120°C. La température de fusion des polymères de la présente invention est classiquement mesurée au pic de fusion dudit polymère par analyse calorimétrique différentielle (DSC) avec une rampe de température de 10°C/min sous atmosphère d'azote.According to one characteristic of the invention, the melting temperature of the apolar polymer may be at least 110 ° C, preferably at least 120 ° C. The melting temperature of the polymers of the present invention is conventionally measured at the melting peak of said polymer by differential scanning calorimetry (DSC) with a temperature ramp of 10 ° C./min under a nitrogen atmosphere.

Selon une autre caractéristique de l'invention, l'indice de fluidité (MFR) (conformément à la norme ASTM D 1238 ou ISO 1133) du polymère apolaire peut être d'au plus 30g/10min (190°C ; 2,16 kg), de préférence d'au plus 20g/10min, et de façon particulièrement préférée d'au plus 10 g/10 min.According to another characteristic of the invention, the melt index (MFR) (according to ASTM D 1238 or ISO 1133) of the apolar polymer may be at most 30 g / 10 min (190 ° C., 2.16 kg). ), preferably at most 20g / 10min, and particularly preferably at most 10g / 10min.

Le polymère apolaire peut être issu d'une polymérisation en présence d'un catalyseur Ziegler-Natta ou Philips conventionnel. De préférence, on utilise un LLDPE Ziegler-Natta. Plus particulièrement, on utilise un LLDPE Ziegler-Natta connu sous le nom de C4-LLDPE ou copolymère d'éthylène et de butène.The apolar polymer may be derived from a polymerization in the presence of a conventional Ziegler-Natta or Philips catalyst. Preferably, a Ziegler-Natta LLDPE is used. More particularly, Ziegler-Natta LLDPE, known as C4-LLDPE or copolymer of ethylene and butene, is used.

Selon un mode de réalisation particulier, la composition comprend en outre un polymère polaire, de préférence au plus 40 parties en poids de polymère polaire pour 100 parties en poids de polymère dans la composition, et de façon particulièrement préférée au plus 20 parties en poids de polymère polaire pour 100 parties en poids de polymère dans la composition. Un polymère polaire dans la composition permet d'améliorer la dispersion des charges électriquement conductrices dans la composition et l'adhésion de la couche externe extrudée sur la gaine extérieure de protection en fonction du caractère polaire ou apolaire de ladite gaine extérieure.According to a particular embodiment, the composition further comprises a polar polymer, preferably at most 40 parts by weight of polar polymer per 100 parts by weight of polymer in the composition, and particularly preferably at most 20 parts by weight of polar polymer per 100 parts by weight of polymer in the composition. A polar polymer in the composition makes it possible to improve the dispersion of the electrically conductive fillers in the composition and the adhesion of the extruded outer layer to the outer protective sheath as a function of the polar or apolar nature of said outer sheath.

A titre d'exemple, le polymère polaire peut être un copolymère d'éthylène acrylate, choisi de préférence parmi les copolymères d'éthylène butyle acrylates (EBA), les copolymères d'éthylène éthyle acrylates (EEA), et les copolymères d'éthylène méthyle acrylates (EMA), ou un de leurs mélanges.By way of example, the polar polymer may be a copolymer of ethylene acrylate, preferably chosen from ethylene butyl acrylate copolymers (EBA), ethylene ethyl acrylate copolymers (EEA), and ethylene copolymers. methyl acrylates (EMA), or a mixture thereof.

Dans un mode de réalisation particulier, la composition de l'invention peut comprendre entre 30 et 90 % en poids de polymère.In a particular embodiment, the composition of the invention may comprise between 30 and 90% by weight of polymer.

La composition peut comprendre au moins 10% en poids de charge électriquement conductrice, de préférence au plus 40% en poids de charge électriquement conductrice, et de façon particulièrement préférée entre 15 et 30% en poids de charge électriquement conductrice.The composition may comprise at least 10% by weight of electrically conductive filler, preferably at most 40% by weight of electrically conductive filler, and particularly preferably preferred between 15 and 30% by weight of electrically conductive filler.

En-dessous de 10 % en poids de charge électriquement conductrice, la conductivité volumique de la composition peut s'avérer insuffisante. En outre, au-dessus de 40 % en poids de charge électriquement conductrice, la préparation ainsi que la mise en oeuvre de la composition peut devenir difficile, et la composition devient également économiquement défavorable.Below 10% by weight of electrically conductive filler, the volume conductivity of the composition may be insufficient. In addition, above 40% by weight of electrically conductive filler, the preparation and the implementation of the composition can become difficult, and the composition also becomes economically unfavorable.

La charge électriquement conductrice peut être choisie parmi du noir de carbone, du graphite, des nanotubes de carbone, des charges inorganiques dopées tels que par exemple de l'oxyde de zinc dopé à l'aluminium ayant une conductivité élevée et linéaire, et des poudres de polymères conducteurs intrinsèques, ou un de leurs mélanges. La charge électriquement conductrice préférée de l'invention est le noir de carbone.The electrically conductive filler may be selected from carbon black, graphite, carbon nanotubes, doped inorganic fillers such as, for example, aluminum-doped zinc oxide having a high and linear conductivity, and powders. intrinsic conductive polymers, or a mixture thereof. The preferred electrically conductive filler of the invention is carbon black.

Les noirs de carbone préférés de l'invention ont les caractéristiques suivantes :

  • une valeur d'absorption d'huile (di(n-butyle)phthalate), selon la norme ASTM D 2414-90, d'au moins 100cm3/100g, et
  • une valeur de surface spécifique BET, selon la norme ASTM D 3037, d'au moins 40 m2/g.
The preferred carbon blacks of the invention have the following characteristics:
  • an oil absorption value (di (n-butyl) phthalate), according to ASTM D 2414-90 standard, of at least 100cm 3 / 100g, and
  • a BET specific surface area value, according to ASTM D 3037, of at least 40 m 2 / g.

La composition selon l'invention peut comprendre en outre d'autres charges, des additifs, des adjuvants, des stabilisants, et/ou des agents de protection contre le vieillissement.The composition according to the invention may further comprise other fillers, additives, adjuvants, stabilizers, and / or anti-aging agents.

Les stabilisants peuvent être typiquement des antioxydants, ces antioxydants étant choisis de préférence parmi les antioxydants phénoliques à encombrement stérique comme par exemple le tetrakismethylene(3,5-di-t-butyl-4-hydroxy-hydrocinnamate)methane, le 2,2'-thiodiethylene bis[3-(3,5-di-ti-butyl-4-hydroxyphenyl) propionate], le 2,2'-Thiobis(6-t-butyl-4-methylphenol) ou le 2,2'-methylenebis(6-t-butyl-4-methylphenol) ; et les antioxydants à base de phosphore comme par exemple le Tris(2,4-di-t-butyl-phenyl)phosphite.The stabilizers may typically be antioxidants, these antioxidants being preferably selected from sterically hindered phenolic antioxidants such as, for example, tetrakismethylene (3,5-di-t-butyl-4-hydroxy-hydrocinnamate) methane, 2,2 ' -thiodiethylene bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2'-Thiobis (6-t-butyl-4-methylphenol) or 2,2'-methylenebis (6-t-butyl-4-methylphenol); and phosphorus-based antioxidants such as, for example, Tris (2,4-di-t-butylphenyl) phosphite.

Le type de stabilisant et son taux dans la composition seront choisis en fonction de la température maximale subie par le polymère pendant la production du mélange et pendant la mise en oeuvre par extrusion sur le câble ainsi que selon la durée maximale d'exposition à cette température.The type of stabilizer and its level in the composition will be chosen according to the maximum temperature experienced by the polymer during the production of the mixture and during the extrusion operation on the cable as well as according to the maximum duration of exposure to this temperature. .

Les agents de protection contre le vieillissement (thermique) peuvent être typiquement des agents de protection contre le vieillissement thermique tels que des quinolines, comme par exemple le poly-2,2,4-trimethyl-1,2-dihydroquinoline (TMQ).The anti-aging agents (thermal) may typically be thermal aging protection agents such as quinolines, for example poly-2,2,4-trimethyl-1,2-dihydroquinoline (TMQ).

Les stabilisants et/ou les agents de protection contre le vieillissement peuvent être ajoutées dans la composition de l'invention dans une quantité d'au plus 2% en poids, de préférence une quantité allant de 0,2 à 1% en poids.Stabilizers and / or anti-aging agents may be added to the composition of the invention in an amount of at most 2% by weight, preferably 0.2 to 1% by weight.

Les autres charges peuvent être des charges minérales sans halogène destinées à améliorer le comportement au feu de la composition, comme par exemple des charges claires, et plus particulièrement des charges ignifugeantes dites charges « HFFR » pour l'anglicisme « Halogen Free Flame Retardant », telles que le trihydrate d'aluminium (ATH), le dihydrate de magnésium (MDH), le trioxyde d'antimoine ou le borate de zinc. Lesdites charges claires peuvent en outre comporter un traitement de surface, pour faciliter par exemple leur incorporation dans le polymère fondu lors du mélange de la composition ou pour augmenter leur efficacité contre les effets du feu. La composition selon l'invention peut ainsi avantageusement comprendre en outre une charge ignifugeante.The other fillers may be halogen-free inorganic fillers intended to improve the fire behavior of the composition, such as, for example, clear fillers, and more particularly flame retardant fillers known as "HFFR" fillers for the " Halogen Free Flame Retardant " anglicism, such as aluminum trihydrate (ATH), magnesium dihydrate (MDH), antimony trioxide or zinc borate. Said clear charges may further comprise a surface treatment, for example to facilitate their incorporation into the polymer melt during the mixing of the composition or to increase their effectiveness against the effects of fire. The composition according to the invention can thus advantageously also comprise a flame-retardant filler.

Les autres charges peuvent également être des charges aptes à réduire le phénomène de gouttes incandescentes lors d'un incendie («anti-drip-agent»), de préférence sans halogène.The other charges may also be charges capable of reducing the phenomenon of incandescent drops during a fire (" anti-drip-agent "), preferably without halogen.

Les autres charges, prises indépendamment les unes des autres ou en combinaison, peuvent être ajoutées dans la composition de l'invention en une quantité d'au plus 50 % en poids, et de préférence en une quantité d'au plus 30% en poids. De préférence, la composition peut comprendre au moins 10% en poids desdites autres charges.The other fillers, taken independently of one another or in combination, can be added to the composition of the invention in an amount of at most 50% by weight, and preferably in an amount of at most 30% by weight. . Preferably, the composition may comprise at least 10% by weight of said other fillers.

Dans un mode de réalisation particulier, la couche externe peut être réticulée ou non.In a particular embodiment, the outer layer may be crosslinked or not.

La couche externe de l'invention a de préférence une épaisseur pouvant être d'au plus 400 µm, et de préférence d'au plus 300 µm. Cette épaisseur est apparentée à une couche externe dite de type « skin ».The outer layer of the invention preferably has a thickness of at most 400 μm, and preferably at most 300 μm. This thickness is related to an outer layer called " skin " type.

La gaine extérieure de protection du câble selon l'invention a de préférence une dureté Shore D d'au moins 50 selon la norme ISO 868.The outer protective sheath of the cable according to the invention preferably has a Shore D hardness of at least 50 according to ISO 868.

L'adhésion de la couche externe peut être améliorée par la nature de la gaine extérieure de protection, notamment lorsque ladite gaine extérieure est de type apolaire, et optionnellement chargée avec des charges minérales, notamment des charges ignifugeantes.The adhesion of the outer layer may be improved by the nature of the outer protective sheath, especially when said outer sheath is apolar type, and optionally loaded with mineral fillers, including flame retardant fillers.

Afin de garantir un câble électrique dit «HFFR» pour l'anglicisme « Halogen Free Flame Retardant », les différentes couches polymériques du câble électrique de l'invention ne comprennent préférentiellement pas de composés halogénés. Ces composés halogénés peuvent être de toutes natures, tels que par exemple des polymères fluorés ou des polymères chlorés comme le polychlorure de vinyle (PVC), des plastifiants halogénés, des charges minérales halogénés, ...etc.In order to guarantee an electric cable called "HFFR" for the Anglicism " Halogen Free Flame Retardant ", the various polymeric layers of the electrical cable of the invention preferably do not include halogenated compounds. These halogenated compounds may be of any kind, such as, for example, fluorinated polymers or chlorinated polymers such as polyvinyl chloride (PVC), halogenated plasticizers, halogenated mineral fillers, etc.

Selon une caractéristique supplémentaire du câble électrique de l'invention, ce dernier comprend en outre un écran semi-conducteur interne entre l'élément conducteur et la couche électriquement isolante, et un écran semi-conducteur externe entre la couche électriquement isolante et l'écran métallique.According to an additional feature of the electrical cable of the invention, the latter further comprises a semiconductor screen internal between the conductive element and the electrically insulating layer, and an external semiconductor screen between the electrically insulating layer and the metal screen.

Le câble électrique ainsi formé est appelé câble d'énergie à haute ou à très haute tension.The electric cable thus formed is called a high or very high voltage power cable.

Un autre objet de l'invention est un procédé de mesure du courant électrique dans la gaine extérieure de protection du câble électrique de l'invention, le procédé comprenant les étapes consistant à :

  1. i. appliquer une tension entre la couche externe extrudée, ladite couche externe étant reliée à la terre, et l'écran métallique du câble électrique, ladite tension étant fournie par une source haute tension à courant continue et à voltage variable, et
  2. ii. faire varier la tension de la source haute tension pour vérifier la stabilité de la tension et les valeurs du courant de charge fournies par la source haute tension afin d'identifier si la gaine extérieure de protection comporte un défaut de structure.
Another object of the invention is a method of measuring the electric current in the outer protective sheath of the electrical cable of the invention, the method comprising the steps of:
  1. i. applying a voltage between the extruded outer layer, said outer layer being grounded, and the metal screen of the electric cable, said voltage being provided by a high voltage DC and variable voltage source, and
  2. ii. varying the voltage of the high voltage source to verify the stability of the voltage and the load current values provided by the high voltage source to identify whether the outer protective sheath has a structural defect.

L'écran métallique peut être mis en contact avec la source haute tension par exemple en découpant une « fenêtre » dans la gaine extérieure de protection pour placer une électrode dans l'écran métallique. La tension est augmentée jusqu'à une valeur prédéterminée, et laissée active pendant une durée prédéterminée. A titre d'exemple, selon la norme NF-C.33.253, la valeur prédéterminée de la tension est fixée à 20 kV et celle de la durée est fixée à 15 minutes.The metal screen can be brought into contact with the high voltage source for example by cutting a "window" in the outer protective sheath to place an electrode in the metal screen. The voltage is increased to a predetermined value, and left active for a predetermined time. By way of example, according to standard NF-C.33.253, the predetermined value of the voltage is set at 20 kV and that of the duration is fixed at 15 minutes.

Lorsque l'on observe une chute de la valeur de la tension ainsi qu'une augmentation et/ou une instabilité du courant de charge débité, la gaine extérieure de protection comporte un défaut. La chute de la valeur de la tension d'une part, et l'augmentation et/ou l'instabilité du courant de charge débité d'autre part, sont facilement identifiables respectivement à l'aide d'un voltmètre haute tension en combinaison avec un réducteur de tension (pour la tension) et d'un shunt ohmique en combinaison avec un voltmètre approprié (pour le courant).When a drop in the value of the voltage is observed as well as an increase and / or an instability of the charged charging current, the outer protective sheath has a defect. The fall of the value of the voltage on the one hand, and the increase and / or the instability of the charge current on the other hand, are easily identifiable respectively using a high voltage voltmeter in combination with a voltage reducer (for voltage) and an ohmic shunt in combination with a suitable voltmeter (for current).

Le défaut peut alors être localisé par exemple par échométrie électrique, puis la partie endommagée du câble peut être réparée.The defect can then be located for example by electrical echometry, then the damaged part of the cable can be repaired.

D'autres caractéristiques et avantages de la présente invention apparaîtront à la lumière de la description d'un exemple non limitatif d'un câble électrique selon l'invention fait en référence à la figure 1.Other characteristics and advantages of the present invention will appear in the light of the description of a non-limiting example of an electric cable according to the invention made with reference to the figure 1 .

La figure 1 illustre une vue schématique en perspective éclatée d'un câble électrique selon un mode de réalisation préféré de l'invention.The figure 1 illustrates a schematic perspective exploded view of an electric cable according to a preferred embodiment of the invention.

Pour des raisons de clarté, seuls les éléments essentiels pour la compréhension de l'invention ont été représentés de manière schématique, et ceci sans respect de l'échelle.For the sake of clarity, only the essential elements for understanding the invention have been shown schematically, and this without respect of the scale.

Le câble d'énergie 1 à haute tension ou à très haute tension, représenté sur la figure 1, comprend un élément conducteur 2 central, notamment en cuivre ou en aluminium, et, successivement et coaxialement autour de cet élément, une couche semi-conductrice 3 dite « interne », une couche électriquement isolante 4, une couche semi-conductrice 5 dite « externe », un écran métallique 6 de mise à la terre et/ou de protection, une gaine extérieure 7 de protection, et une couche externe 8 extrudée conforme à l'invention.The power cable 1 at high voltage or at very high voltage, represented on the figure 1 , comprises a central conducting element 2, in particular made of copper or aluminum, and, successively and coaxially around this element, a so-called "internal" semiconductor layer 3, an electrically insulating layer 4, a semiconductor layer 5 called " external ", a metal screen 6 of grounding and / or protection, an outer sheath 7 of protection, and an outer layer 8 extruded according to the invention.

Les couches 3, 4 et 5 sont classiquement des couches extrudées et réticulées par des procédés bien connus de l'homme du métier.Layers 3, 4 and 5 are conventionally extruded and crosslinked layers by methods well known to those skilled in the art.

La présence des couches semi-conductrices 3 et 5 est préférentielle, mais non essentielle. La structure de protection, qui comporte l'écran métallique 6 et la gaine extérieure 7 de protection, peut également comporter d'autres éléments de protection. La structure de protection de ce câble est en tant que telle de type connu et hors du cadre de la présente invention.The presence of the semiconductor layers 3 and 5 is preferred, but not essential. The protective structure, which includes the metal screen 6 and the outer sheath 7 protection, may also include other protective elements. The protective structure of this cable is as such of known type and outside the scope of the present invention.

ExemplesExamples

  • Composition 1 (essai comparatif) : composition semi-conductrice thermoplastique commercialisée par la société DOW Chemicals sous la référence DHDA 7708-BK.Composition 1 (comparative test): thermoplastic semiconductive composition marketed by DOW Chemicals under the reference DHDA 7708-BK.
  • Composition 2 (essai comparatif) : composition semi-conductrice thermoplastique commercialisée par la Kyungwon New Materials Inc sous la référence Pramkor 7001.Composition 2 (comparative test): thermoplastic semiconductor composition marketed by Kyungwon New Materials Inc under the reference Pramkor 7001.
  • Composition 3 : composition comprenant :
    • 74,5 % en poids de LLDPE (polymère thermoplastique apolaire), commercialisé par la société Polimeri Europa SpA sous la référence Flexirène CL10 (densité = 0,918 g/cm3 ; Indice de fluidité MFR = 2,6 g/10 min ; température de fusion = 121°C),
    • 25 % en poids de noir de carbone commercialisé par la société Cabot Corporation sous la référence Vulcan XC-500, et
    • 0,5 % en poids d'un antioxydant commercialisé par la société Flexsys N.V. sous la référence Flektol TMQ.
    Composition 3: composition comprising:
    • 74.5% by weight of LLDPE (apolar thermoplastic polymer), marketed by Polimeri Europa SpA under the reference Flexirene CL10 (density = 0.918 g / cm 3 ; melt flow rate MFR = 2.6 g / 10 min; melting = 121 ° C),
    • 25% by weight of carbon black marketed by Cabot Corporation under the reference Vulcan XC-500, and
    • 0.5% by weight of an antioxidant marketed by Flexsys NV under the reference Flektol TMQ.
  • Composition 4 : composition comprenant :
    • 54,8 % en poids de LLDPE (polymère thermoplastique apolaire), commercialisé par la société Polimeri Europa SpA sous la référence Flexirène CL10 (densité = 0,918 g/cm3 ; Indice de fluidité MFR = 2,6 g/10 min ; température de fusion = 121°C),
    • 29,8 % en poids de dihydrate de magnésium (MDH), commercialisé par la société Albemarle Coporation sous la référence Magnifin H5A,
    • 15 % en poids de noir de carbone, commercialisé par la société Cabot Corporation sous la référence Vulcan XC-72, et
    • 0,4 % en poids d'un antioxydant, commercialisé par la société Ciba Specialty Chemicals Inc. sous la référence Irganox 1010FF.
    Composition 4: composition comprising:
    • 54.8% by weight of LLDPE (apolar thermoplastic polymer), marketed by Polimeri Europa SpA under the reference Flexirene CL10 (density = 0.918 g / cm 3, melt flow rate MFR = 2.6 g / 10 min, melting temperature = 121 ° C),
    • 29.8% by weight of magnesium dihydrate (MDH), marketed by Albemarle Coporation under the reference Magnifin H5A,
    • 15% by weight of carbon black, marketed by Cabot Corporation under the reference Vulcan XC-72, and
    • 0.4% by weight of an antioxidant marketed by Ciba Specialty Chemicals Inc. under the reference Irganox 1010FF.
  • Composition 5 : composition comprenant :
    • 49,6 % en poids de LLDPE (polymère thermoplastique apolaire), commercialisé par la société Polimeri Europa SpA sous la référence Flexirène CL10 (densité = 0,918 g/cm3 ; Indice de fluidité MFR = 2,6 g/10 min ; température de fusion = 121°C),
    • 35,0 % en poids de dihydrate de magnésium (MDH), commercialisé par la société Albemarle Coporation sous la référence Magnifin H5A,
    • 15 % en poids de noir de carbone, commercialisé par la société Cabot Corporation sous la référence Vulcan XC-72, et
    • 0,4 % en poids d'un antioxydant commercialisé par la société Ciba Specialty Chemicals Inc. sous la référence Irganox 1010FF.
    Composition 5: Composition comprising:
    • 49.6% by weight of LLDPE (apolar thermoplastic polymer), sold by the company Polimeri Europa SpA under the reference Flexirene CL10 (density = 0.918 g / cm 3, melt flow rate MFR = 2.6 g / 10 min, melting temperature = 121 ° C),
    • 35.0% by weight of magnesium dihydrate (MDH), marketed by Albemarle Coporation under the reference Magnifin H5A,
    • 15% by weight of carbon black, marketed by Cabot Corporation under the reference Vulcan XC-72, and
    • 0.4% by weight of an antioxidant marketed by Ciba Specialty Chemicals Inc. under the reference Irganox 1010FF.

Les compositions 1 à 5 sont mélangées dans un mélangeur continu ou une extrudeuse bi-vis. Le polymère, et éventuellement les additifs, sont introduits par des moyens de dosage appropriés dans le mélangeur, le polymère étant mis à l'état fondu. Ensuite, les charges électriquement conductrices, et éventuellement les autres charges, sont introduites dans la masse fondue et homogénéisées. Le mélange obtenu est granulé à l'aide d'un dispositif de granulation.The compositions 1 to 5 are mixed in a continuous mixer or a twin-screw extruder. The polymer, and optionally the additives, are introduced by appropriate metering means into the mixer, the polymer being melt. Then, the electrically conductive charges, and possibly the other charges, are introduced into the melt and homogenized. The mixture obtained is granulated using a granulation device.

Les granulés obtenus à l'étape de granulation sont extrudés, l'extrudat étant déposé autour d'une gaine extérieure de protection (également extrudée) d'une épaisseur de 2 à 3 mm entourant un fil métallique d'une section de 1,5 mm2. L'épaisseur respective des couches externes, obtenues respectivement à partir des compositions 1 à 3 extrudées, est comprise entre 0,15 et 0,2 mm.The granules obtained in the granulation step are extruded, the extrudate being deposited around an outer protective sheath (also extruded) with a thickness of 2 to 3 mm surrounding a wire of a section of 1.5 mm 2 . The respective thickness of the outer layers, obtained respectively from compositions 1 to 3 extruded, is between 0.15 and 0.2 mm.

Les bicouches des câbles électriques ainsi obtenus sont soumises à un contrôle visuel.The bilayers of the electric cables thus obtained are subjected to a visual inspection.

La nature des gaines de protections constitutives des bicouches est rassemblée dans le tableau 1 ci-après. Tableau 1 Composition 1 Composition 2 Composition 3 Composition 4 Composition 5 Gaine HFFR Détachement important de la couche externe Détachement important de la couche externe Aucun détachement de la couche externe NM* Aucun détachement de la couche externe *NM = caractéristique non mesurée The nature of the protective sheaths constituting the bilayers is summarized in Table 1 below. <b><u> Table 1 </ u></b> Composition 1 Composition 2 Composition 3 Composition 4 Composition 5 HFFR sheath Significant detachment of the outer layer Significant detachment of the outer layer No detachment of the outer layer NM * No detachment of the outer layer * NM = unmeasured characteristic

La gaine HFFR (ou gaine extérieure de protection) du tableau 1 est un matériau HFFR commercialisé par la société NEXANS sous la référence HS3411-T.The HFFR sheath (or outer protective sheath) of Table 1 is an HFFR material marketed by NEXANS under the reference HS3411-T.

Au vu des résultats qualitatifs visuels rassemblés dans le tableau 1, seule les compositions thermoplastiques de l'invention peuvent s'extruder sur la gaine extérieure de protection du câble sans qu'un détachement important de la couche externe ne puisse être constaté, contrairement aux compositions 1 et 2. Tableau 2 Composition 1 Composition 2 Composition 3 Composition 4 Composition 5 Résistance à la rupture (MPa) 11,7 29,8 24,2 16,5 15,5 Allongement à la rupture (%) 450 513 575 518 454 Module d'élasticité (MPa) NM* 1620 1046 1056 1267 Résistivité volumique à 23°C (Ohm.m) 0,25 10 0,22 0,36 0,25 Dureté (Shore D) 55 NM* 57 NM* NM* Durée de combustion en sens vertical de joncs pleins (secondes) NM* NM* 259 298 366 Appréciation de la mise à feu lors du test de combustion de joncs pleins NM* NM* Mise à feu facile Mise à feu moyenne Mise à feu difficile *NM = Valeur ou caractéristique non mesurée In view of the qualitative visual results summarized in Table 1, only the thermoplastic compositions of the invention can be extruded on the outer protective sheath of the cable without significant detachment of the outer layer can be found, unlike compositions 1 and 2. <b><u> Table 2 </ u></b> Composition 1 Composition 2 Composition 3 Composition 4 Composition 5 Resistance to fracture (MPa) 11.7 29.8 24.2 16.5 15.5 Elongation at break (%) 450 513 575 518 454 Modulus of elasticity (MPa) NM * 1620 1046 1056 1267 Volume resistivity at 23 ° C (Ohm.m) 0.25 10 0.22 0.36 0.25 Hardness (Shore D) 55 NM * 57 NM * NM * Burn time in vertical direction of solid rods (seconds) NM * NM * 259 298 366 Evaluation of the firing during the test of burning of solid rods NM * NM * Easy firing Medium firing Difficult firing * NM = Value or characteristic not measured

Les propriétés mécaniques (résistance à la rupture, allongement à la rupture et module d'élasticité) ainsi que la résistivité volumique à 23°C ont été mesurées sur des éprouvettes prélevées dans des rubans extrudés (d'une épaisseur de 0,3 mm) obtenus à partir des compositions 1 à 5.The mechanical properties (tensile strength, elongation at break and modulus of elasticity) as well as the volume resistivity at 23 ° C were measured on specimens taken from extruded strips (0.3 mm thick) obtained from compositions 1 to 5.

La résistance à la rupture et l'allongement à la rupture sont déterminées selon la norme IEC 60811-1-1, les éprouvettes étant du type « haltères » ISO 37-2 et la vitesse de traction utilisée étant de 100 mm/min.The breaking strength and elongation at break are determined according to IEC 60811-1-1 standard, the specimens being of the type "dumbbells" ISO 37-2 and the tensile speed used being 100 mm / min.

Le module d'élasticité (ou Module de Young) est quant à lui déterminé par des essais de traction selon la norme ISO 527-1 ou ASTM D 638, les éprouvettes étant du type « haltères » ISO 37-2 et la vitesse de traction utilisée étant de 100 mm/min. Le module d'élasticité permet de caractériser la rigidité d'un matériau. Plus sa valeur est élevée, plus la matière est dite rigide.The modulus of elasticity (or Young's modulus) is determined by tensile tests according to ISO 527-1 or ASTM D 638, the specimens being of the type "dumbbells" ISO 37-2 and the traction speed used being 100 mm / min. The modulus of elasticity makes it possible to characterize the rigidity of a material. The higher its value, the more the material is said to be rigid.

La résistivité volumique est déterminée selon la norme ASTM D991 ou une méthode dérivée de la norme ISO 3915.The volume resistivity is determined according to the ASTM D991 standard or a method derived from the ISO 3915 standard.

La valeur Shore D est déterminée à l'aide d'un duromètre, suivant la norme ISO868 ou ASTM D 2240.The Shore D value is determined using a durometer, according to ISO868 or ASTM D 2240.

La durée de combustion en sens vertical d'une flamme de joncs pleins est déterminée de la façon suivante. Des joncs pleins d'un diamètre de 4 mm sont extrudés avec chacune des compositions 1 à 5. Ces joncs sont ensuite séchés pendant 48 h à une température de 70°C dans une étuve à air chaud pour éliminer une éventuelle influence d'humidité absorbée sur le comportement au feu. Après séchage, les joncs sont découpés en morceaux d'une longueur de 22 cm. Sous une hotte d'aspiration de fumées est placé un statif de laboratoire sur lequel est fixé une noix de serrage à une hauteur de 30 cm. Cette noix de serrage tient une courte tige de statif dans le sens horizontal. A l'extrémité de cette tige, une deuxième noix de serrage est fixée. Chaque jonc est fixé verticalement dans cette deuxième noix de serrage, la longueur de serrage étant de 2 cm. La longueur libre disponible pour la flamme est ainsi de 20 cm. Le jonc est ensuite mis à feu à l'aide d'une flamme de butane. Le temps entre la mise à feu du jonc (c'est-à-dire du moment où le jonc brûle tout seul) et l'extinction complète de la flamme, est mesuré à l'aide d'un chronomètre. Pour chacune des compositions testées, 3 joncs sont brûlés et la valeur moyenne des durées de combustion ainsi obtenues calculée (en secondes). L'interprétation des valeurs est comme telle: plus la durée de combustion est longue, et ceci uniquement pour une combustion sur toute la longueur et où le jonc est consumé en totalité sur 20 cm, plus la charge ignifugeante est efficace pour retarder la combustion.The burning time in the vertical direction of a flame of solid rods is determined as follows. Solid rods with a diameter of 4 mm are extruded with each of compositions 1 to 5. These rods are then dried for 48 hours at a temperature of 70 ° C. in a hot air oven to eliminate any influence of absorbed moisture. on fire behavior. After drying, the rushes are cut into pieces with a length of 22 cm. Under a fume hood is placed a laboratory stand on which is fixed a clamping nut at a height of 30 cm. This clamping nut holds a short stand rod in the horizontal direction. At the end of this rod, a second clamping nut is fixed. Each ring is fixed vertically in this second clamping nut, the clamping length being 2 cm. The free length available for the flame is thus 20 cm. The ring is then fired with a butane flame. The time between the firing of the rod (that is to say when the rod burns all alone) and the complete extinction of the flame, is measured using a stopwatch. For each of the compositions tested, 3 rods are burned and the average value of the combustion times thus obtained calculated (in seconds). The interpretation of the values is as such: the longer the burning time, and this only for a combustion on the entire length and where the rod is consumed in total over 20 cm, the fire retardant filler is effective to delay combustion.

Pour apprécier le cas possible d'une extinction de la flamme avant que le jonc soit consumé (qui représenterait le cas le plus favorable), on introduit le critère de l'appréciation de la mis à feu (lors du test de combustion de joncs pleins). Plus cette mise à feu est difficile, plus l'effet de retardation au feu est prononcé.To assess the possible case of extinguishing the flame before the rod is consumed (which would be the most favorable case), we introduce the criterion of the evaluation of the firing (during the test of combustion of solid rods ). The more difficult this firing is, the more pronounced the effect of fire retardation.

Les résultats rassemblés dans le tableau 2 montrent que les compositions 3 à 5 selon l'invention présente des propriétés mécaniques et de résistivité améliorées de façon significative par rapport aux essais comparatifs, tout en gardant une très bonne adhésion sur la gaine extérieure de protection (voir résultats du tableau 1).The results compiled in Table 2 show that the compositions 3 to 5 according to the invention have significantly improved mechanical and resistivity properties compared to the comparative tests, while keeping a very good adhesion to the outer protective sheath (see FIG. results from Table 1).

Quant au module d'élasticité, les valeurs plus faibles des compositions 3 à 5 par rapport à composition 2 montrent que les compositions selon l'invention sont bien plus flexibles mécaniquement, même pour les compositions 4 et 5 fortement chargées. Cette flexibilité accrue réduit le risque de fissuration de la couche externe lors de la manipulation et/ou de l'installation du câble.As for the modulus of elasticity, the lower values of compositions 3 to 5 compared to composition 2 show that the compositions according to the invention are much more mechanically flexible, even for compositions 4 and 5 which are heavily loaded. This increased flexibility reduces the risk of cracking of the outer layer during handling and / or installation of the cable.

Les compositions 4 et 5 contenant en plus une charge ignifugeante du type HFFR montrent un effet retardant à la flamme accru par rapport à composition 3, particulièrement prononcé pour la composition 5.Compositions 4 and 5 additionally containing a flame retardant filler of the HFFR type show an increased flame retardancy effect with respect to composition 3, which is particularly pronounced for composition 5.

Ainsi, le comportement au feu de l'ensemble constitué par ladite couche externe conductrice selon l'invention et par la gaine extérieure de protection de type HFFR, est très favorable, ledit ensemble présentant en outre de très bonnes propriétés mécaniques, une bonne conductivité électrique ainsi qu'une bonne adhésion.Thus, the fire behavior of the assembly consisting of said conductive outer layer according to the invention and the outer protective sheath type HFFR, is very favorable, said assembly also having very good mechanical properties, good electrical conductivity as well as a good membership.

Claims (12)

  1. Electrical cable (1) comprising a conductive element (2), and successively around this conductive element (2), an electrically-insulating layer (4), a metal screen (6) and an outer protective sheath (7), characterized in that it further comprises an extruded outer layer (8) surrounding the outer protective sheath (7), wherein the extruded outer layer (8) is in direct contact with the outer protective sheath (7), and is obtained from a composition comprising more than 50.0 parts by weight of apolar polymer per 100 parts by weight of polymer in the composition, and an electrically-conductive filler.
  2. Cable according to claim 1, characterized in that the composition comprises at least 60 parts by weight of apolar polymer per 100 parts by weight of polymer in the composition, preferably at least 80 parts by weight of apolar polymer per 100 parts by weight of polymer in the composition.
  3. Cable according to claim 1 or 2, characterized in that the apolar polymer is selected from among linear low density polyethylenes (LLDPE), very low density polyethylenes (VLDPE), and ultra low density polyethylenes (ULDPE), or one of their mixtures.
  4. Cable according to any one of the preceding claims, characterized in that the composition further comprises at most 40 parts by weight of polar polymer per 100 parts by weight of polymer in the composition, preferably at most 20 parts by weight of polar polymer per 100 parts by weight of polymer in the composition.
  5. Cable according to claim 4, characterized in that the polar polymer is selected from among copolymers of ethylene butyl acrylate (EBA), copolymers of ethylene ethyl acrylates (EEA), and copolymers of ethylene methyl acrylates (EMA), or one of their mixtures.
  6. Cable according to any one of the preceding claims, characterized in that the composition comprises at least 10% by weight of electrically-conductive filler.
  7. Cable according to any one of the preceding claims, characterized in that the composition comprises at most 40% by weight of electrically-conductive filler.
  8. Cable according to any one of the preceding claims, characterized in that the electrically-conductive filler is selected from among carbon black, graphite, carbon nanotubes, doped inorganic fillers, and intrinsically-conductive polymer powders, or one of their mixtures.
  9. Cable according to any one of the preceding claims, characterized in that the outer layer (8) has a thickness of at most 400 µm, preferably at most 300 µm.
  10. Cable according to any one of the preceding claims, characterized in that the outer protective sheath has a Shore D hardness of at least 50 according to ISO 868.
  11. Cable according to any one of the preceding claims, characterized in that it further comprises an internal semiconductor screen (3) between the conductive element (2) and the electrically-insulating layer (4), and an external semiconductor screen (5) between the electrically-insulating layer (4) and the metal screen (6).
  12. Cable according to any one of the preceding claims, characterized in that the composition further comprises a flame retardant filler.
EP10154403.9A 2009-02-27 2010-02-23 High voltage electrical cable Revoked EP2224459B1 (en)

Applications Claiming Priority (1)

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FR0951257A FR2942673B1 (en) 2009-02-27 2009-02-27 HIGH VOLTAGE ELECTRICAL CABLE

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EP2224459B1 true EP2224459B1 (en) 2018-12-12

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FR2942673B1 (en) 2011-04-01
FR2942673A1 (en) 2010-09-03

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