EP2319053B1 - Ceramisable composition for a power and/or telecommunication cable - Google Patents

Ceramisable composition for a power and/or telecommunication cable Download PDF

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Publication number
EP2319053B1
EP2319053B1 EP09737074A EP09737074A EP2319053B1 EP 2319053 B1 EP2319053 B1 EP 2319053B1 EP 09737074 A EP09737074 A EP 09737074A EP 09737074 A EP09737074 A EP 09737074A EP 2319053 B1 EP2319053 B1 EP 2319053B1
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Prior art keywords
weight
compound
composition
cable according
compounds
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EP09737074A
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German (de)
French (fr)
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EP2319053A1 (en
Inventor
Christelle Mazel
Arnaud Piechaczyk
Roland Avril
Stéphanie HOAREAU
Melek Kirli
Elisabeth Tavard
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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
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/292—Protection against damage caused by extremes of temperature or by flame using material resistant to heat
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame

Definitions

  • the present invention relates to an energy and / or telecommunication cable comprising at least one electrically insulating layer which is also able to withstand extreme thermal conditions.
  • safety cables that is to say to energy or telecommunication cables intended to remain operational for a defined time when they are subjected to high heat and / or or directly to the fire.
  • a significant slowdown in the progression of the flames it is as much time gained to evacuate the places and / or to implement appropriate means of extinction.
  • the cable In case of fire, the cable must be able to withstand the fire in order to operate as long as possible and limit its degradation.
  • a safety cable must also not be dangerous for its environment, that is to say, not to release toxic fumes and / or too opaque when subjected to extreme thermal conditions.
  • a cable is schematically constituted of at least one conductive element, electrical or optical, surrounded by at least one electrically insulating layer.
  • the electrically insulating layer may be an insulation directly in contact with at least one conductive element of the cable. It can also be a protective sheath surrounding one or more insulated conductive elements.
  • a known fire-resistant cable insulating layer composition is described in the document WO 2004/035711 .
  • This composition comprises an organic polymer and several inorganic fillers which may be in particular mica, zinc borate, and metal oxides such as oxides of calcium, iron, magnesium, aluminum, zirconium, zinc, zinc tin or barium.
  • JP 2004-95373 discloses an insulating strip for flat flexible cable having flame retardance properties comprising as essential elements a polyester resin and a metal hydroxide.
  • the object of the present invention is to overcome the drawbacks of the solutions of the state of the art by providing in particular a cable comprising an insulating layer having an optimal compromise between its electrical insulation properties and mechanical strength in extreme thermal conditions. .
  • This combination of inorganic fillers (compounds b, c and d) is optimally adapted to react in the conditions of a fire and thus form a refractory ceramic compound: the insulating layer is said to be ceramizable.
  • the cable according to the present invention satisfies in particular the standards IEC 60331 part 21 or 23, DIN 4102 part 12 and EN 50200.
  • precursor of a metal oxide x (precursor of potassium oxide, boron oxide or calcium oxide) are understood to mean any inorganic element capable of forming under the action of an elevation temperature said metal oxide x.
  • said inorganic element forms the metal oxide at a temperature T lower than the temperature Tc of (beginning of) ceramization of the insulating layer.
  • the ceramization start temperature is considered to be the temperature sufficient to observe the rearrangement and sticking of the particles set forth in step i above.
  • It can be any type of organic polymer well known to those skilled in the art, especially capable of being extruded, of the thermoplastic or elastomeric polymer type.
  • the organic polymer may be a mixture of several organic polymers, or may be a mixture of polymers consisting of at least one major organic polymer in the mixture and at least one other polymer of different nature.
  • the organic polymer is preferably selected from an olefin polymer, an acrylate or methacrylate polymer, a vinyl polymer, and a fluoropolymer, or a mixture thereof.
  • the olefin polymer is especially chosen from a homopolymer or copolymer of ethylene, and a homopolymer or copolymer of propylene, or a mixture thereof.
  • the olefin polymer is chosen from an ethylene homopolymer, an ethylene-octene (PEO) copolymer, an ethylene-vinyl acetate (EVA) copolymer, a copolymer of propylene diene monomer (EPDM), a copolymer of ethylene and methyl acrylate (EMA), a copolymer of ethylene and butyl acrylate (EBA), and a copolymer of ethylene and acrylate ethyl (EEA), or a mixture thereof.
  • the compound b may advantageously be a potassium oxide as such or a phyllosilicate comprising a potassium oxide. More particularly, the phyllosilicate comprising a potassium oxide is preferably an aluminum phyllosilicate comprising a potassium oxide.
  • the potassium oxide preferably has the following chemical formula: K 2 O.
  • Other types of potassium oxides such as, for example, complex oxides, or in other words polyoxometalates, can also be considered in the context of the present invention. of the invention.
  • the phyllosilicates comprising a potassium oxide may be certain types of mica such as micas aluminoceladonite, boromuscovite, celadonite, chromphyllite, ferroaluminoceladonite, ferrocelatonite, muscovite, roscoelite, annite, biotite, eastonite, hendricksite, lepidolite, masutomilite, montdorite, norrishite , polylithionite, phlogopite, siderophyllite, tainiotite, tetra-ferri-annite, tetra-ferriphlogopite, trilithionite, zinnwaldite, anadite, glauconite, or illite.
  • Aluminum phyllosilicates comprising a potassium oxide such as micas aluminoceladonite, chromphyllite, ferroaluminoceladonite, muscovite, roscoelite, annite, biotite, eastonite, hendricksite, lepidolite, masutomilite, montdorite, polylithionite, phlogopite, siderophyllite, trilithionite, are preferred. zinnwaldite, anadite, glauconite, or illite.
  • a potassium oxide such as micas aluminoceladonite, chromphyllite, ferroaluminoceladonite, muscovite, roscoelite, annite, biotite, eastonite, hendricksite, lepidolite, masutomilite, montdorite, polylithionite, phlogopite, siderophyllite, trilith
  • aluminum phyllosilicates comprising a potassium oxide, the muscovite mica of the chemical formula 6SiO 2 -3AbO 3 -K 2 O-2H 2 O or the phlogopite mica of the chemical formula 6SiO 2 -AbO 3 -K 2 O- 6MgO-2H 2 O.
  • the amount of the compound b may be at least 2 parts by weight, preferably at least 3 parts by weight, and still more preferably at least 6 parts by weight, per 100 parts by weight of polymer (s) in the composition .
  • the amount of the compound b may be at least 2% by weight, preferably at least 5% by weight, and still more preferably at least 10% by weight, of the total weight of the compounds b, c and d in the composition.
  • the boron oxide may typically have the following formula: B 2 O 3 .
  • B 2 O 3 does not exist in this form in the free state.
  • a boron oxide precursor is generally used.
  • the precursor of boron oxide may be chosen for example from zinc borate, boron phosphate, boric acid, calcium borate (eg colemanite of chemical formula Ca 2 B 6 O 11 , 5H 2 O) and sodium borate (eg borax of the chemical formula Na 2 B 4 O 7 , 10H 2 O).
  • the boron oxide precursor is preferably dehydrated, especially when said precursor is zinc borate, in order to avoid dehydration of said precursor when the insulating layer is subjected to fire and thus to disturb the dimensional stability of the ceramic formed.
  • the amount of compound c may be at least 20 parts by weight, and preferably at least 25 parts by weight, per 100 parts by weight of polymer (s) in the composition.
  • the amount of compound c may be at least 10% by weight, preferably at least 15% by weight, and more preferably at least 20% by weight, of the total weight of compounds b, c and d in the composition.
  • One of the calcium oxide precursors CaO may be calcium carbonate. Between calcium oxide, a calcium oxide precursor and the calcium oxide and calcium oxide precursor mixture, calcium oxide as such is preferred.
  • the amount of the compound d may advantageously be at least 10 parts by weight, preferably at least 20 parts by weight, and still more preferably at least 25 parts by weight, per 100 parts by weight of polymer (s) in the composition.
  • the amount of the compound d can advantageously be at least 15% by weight, and preferably at least 20% by weight, of the total weight of the compounds b, c and d in the composition.
  • Potassium oxide is present in some types of mica as mentioned above.
  • the amount of compound b can be at least 40% by weight, the total weight of compounds b, c and d in the composition.
  • the composition may comprise an amount of compound b at most 80% by weight, an amount of compound c at most 30% by weight, and an amount of the compound of at most 50% by weight, said amounts being defined with respect to the total weight of compounds b, c and d in the composition.
  • the composition can thus comprise an amount of compound b of 40 to 80% by weight, an amount of compound c of 10 to 30% by weight, and an amount of compound d of 10 to 50% by weight, said amounts being defined relative to the total weight of compounds b, c and d in the composition.
  • the composition comprises an amount of the compound b of 60% by weight, a quantity of the compound c of 20% by weight, and a quantity of the compound d of 20% by weight, said amounts being defined in relation to the total weight of compounds b, c and d in the composition.
  • composition according to the present invention may furthermore comprise other inorganic fillers of the nanoparticle type.
  • Said nanoparticles typically have at least one of their nanometric dimensions (10 -9 meters). More particularly, the average size of the mineral nanoparticles is at most 400 nm, preferably at most 300 nm, and more preferably at most 100 nm.
  • the average size of the nanoparticles is conventionally determined by methods that are well known to those skilled in the art, for example by laser granulometry or by microscopy techniques, in particular by SEM (Scanning Electron Microscopy) or TEM (Transmission Electron Microscopy).
  • These nanoparticles preferably have a form factor of at least 100, the form factor being the ratio of the largest dimension of a mineral nanoparticle to the smallest dimension of said nanoparticle.
  • the nanoparticles are phyllosilicates chosen in particular from montmorillonites, sepiolites, illites, attapulgites, talcs, and kaolins, or a mixture thereof.
  • the composition does not comprise halogenated inorganic fillers.
  • the composition may furthermore not include halogenated polymers such as, for example, fluorinated polymers or chlorinated polymers such as polyvinyl chloride (PVC).
  • the amounts of inorganic fillers in the composition can be defined in that the composition comprises at least 20 parts by weight, preferably at least 40 parts by weight preferably at least 60 parts by weight, and even more preferably at least 90 parts by weight of inorganic fillers, per 100 parts by weight of polymer (s).
  • the lower limit of 90 parts by weight is especially taken into account when the compound b is mica (i.e. phyllosilicate comprising a potassium oxide).
  • the composition comprises at most 200 parts by weight of inorganic fillers per 100 parts by weight of polymer (s), in order to limit the problems of rheologies in the composition.
  • the composition may be crosslinked to obtain a crosslinked insulating layer.
  • the crosslinking of the composition can be carried out by conventional crosslinking techniques well known to those skilled in the art such as, for example, silane crosslinking in the presence of a crosslinking agent, peroxide crosslinking under the action of heat, or photochemically cross-linking such as irradiation with beta radiation, or irradiation with ultraviolet radiation in the presence of a photoinitiator.
  • the figure 1 represents an electric cable 1 comprising a solid-type conducting element 2, surrounded by an insulating-type insulating layer 3 directly in contact with the conductive element, the latter being itself surrounded by an insulating layer of the protective sheath type 4.
  • the figure 2 also represents an electrical cable 10 comprising at least two conductive elements 12 of multi-strand type. Each strand 12 is surrounded by an insulation insulating layer 13 directly in contact with the conductive element, all of these isolated strands being surrounded by an insulating layer of the protective sheath type 14.
  • the insulating layer 3, 13 and / or the protective sheath 4, 14 can be obtained from the composition according to the present invention.
  • the insulation 3, 13 has a thickness of 0.6 to 2.4 mm and the protective sheath 4, 14 has a thickness of 1 to 2.5 mm.
  • composition according to the invention is conventionally shaped by extrusion around or conductive elements to form the insulation 3, 13 and / or the protective sheath 4, 14.
  • the extrusion of said composition may be an extrusion said compression or stuffing, or a so-called tubing extrusion.
  • the tubular extrusion makes it possible to obtain a tubular insulating layer, that is to say a tube-shaped layer of a certain thickness whose inner surface and the outer surface are respectively two substantially concentric cylinders.
  • the tubular insulating layer does not fill the interstices between the conductive elements (isolated or not) and thus provides empty spaces between it and the insulated or insulated conductive elements that it surrounds, especially the empty spaces occupy at least 10% of the section of the cable.
  • the insulating layer leaves the free conductive elements within said layer.
  • the stuffing extrusion makes it possible to obtain a stuffing layer, that is to say a layer filling the interstices between the conductive elements (isolated or not) whose volumes are accessible, and thus said layer is directly in contact with the elements isolated conductors or not.
  • Tables 1a and 1b below detail the compositions used to obtain said insulating layers.
  • the composition may typically further comprise additives in an amount of from 5 to 20 phr.
  • additives are well known to those skilled in the art and may be chosen for example from protection agents (antioxidants, anti-UV, anti-copper), processing agents (plasticizers or lubricants), and pigments .
  • melt polymer (s) is continuously blended with the various inorganic fillers detailed in Tables 1a and 1b.
  • the mixing is carried out using a Buss single-screw mixer or a twin-screw extruder and the inorganic fillers are added to the polymer (s) using a conventional metering hopper.
  • the mixture of the charged polymer (s) is extruded directly onto a solid or multi-stranded copper wire with a cross-section of 1.5 mm 2 , the extruded insulating layer having a thickness of 0.8 mm.
  • the polymers of Table 1a in the molten state are continuously mixed and heated with a silane crosslinking agent of the alkoxysilane or carboxysilane type together with an organic peroxide, using a Buss single-screw mixer or of a twin-screw extruder.
  • the crosslinking agent is added in an amount of 1 to 2.5% and that used in the compositions B1 to B4 is Silfin 59 sold by the company Evonik.
  • the temperature of the mixture of this first step is such that it typically allows the polymer mixture to be used while decomposing the organic peroxide.
  • This first step makes it possible to obtain a mixture of silane graft polymers in the form of granules.
  • the molar silane graft polymer is continuously blended and heated to the various inorganic fillers detailed in Table 1a.
  • This second step makes it possible to obtain a grafted silane graft polymer, the charged silane graft polymer being typically obtained in the form of granules.
  • the granules of charged silane graft polymer are used in the molten state in a single-screw extruder in the presence of a catalyst for the condensation reaction of silanol groups, such as, for example, dibutyltin dilaurate. (DBTL) well known to those skilled in the art.
  • DBTL dibutyltin dilaurate.
  • the catalyst is typically added to the charged silane graft polymer in the form of a masterbatch based on a polyolefin compatible with said graft polymer.
  • the masterbatch containing said catalyst is added in an amount of about 2% by weight to the loaded silane graft polymer.
  • the mixture of the charged silane graft polymer and the silanol condensation catalyst is extruded directly onto a 1.5 mm 2 multi-stranded copper wire, the extruded insulating layer having a thickness of 0.8 mm.
  • melt polymer (s) is continuously blended with the various inorganic fillers and peroxide detailed in Table 1a.
  • the mixing is carried out using a Buss single-screw mixer or a twin-screw extruder and the inorganic fillers and peroxide are added to the polymer (s) using a conventional metering hopper.
  • the mixture of the charged polymer (s) is extruded directly onto a solid or multi-stranded copper wire with a cross-section of 1.5 mm 2 , the extruded insulating layer having a thickness of 0.8 mm.
  • the mixing and extrusion temperature conditions are such that the temperature is sufficient to soften and homogenize the peroxide and the inorganic fillers in the polymer (s) while avoiding initiating the decomposition of the peroxide.
  • the insulating layer thus formed is crosslinked by the peroxide route under the action of heat, in a salt bath, in a vapor tube or in a fluidized bed at atmospheric pressure or at a pressure close to the latter.
  • the fire resistance tests are carried out according to the following three standards: IEC 60331 part 21 or 23, DIN 4102 part 12, and EN 50200.
  • the standard IEC 60331 part 21 or 23 consists of subjecting an electric cable to its nominal voltage when it is suspended horizontally over a flame of at least 750 ° C for a determined period but without mechanical stress.
  • This period is checked whether there is a short-circuit or breakage of the electrical conductors.
  • the test is successful when there is no short circuit or breakage of the electrical conductors during the test and the next 15 minutes.
  • the electrical cable that has passed the test for 30 minutes is then classified FE30. When it passes the test for 90 minutes or 180 minutes, it is respectively classified FE90 and FE180.
  • DIN 4102 part 12 consists in subjecting an electric cable with its fixing devices in an oven of at least 3 meters in length for a determined period of time according to a standard temperature curve (ISO 834).
  • the electrical cable having passed the test for 30 minutes at 842 ° C is then classified E30.
  • it passes the test for 60 minutes at 945 ° C or for 90 minutes at 1006 ° C it is then respectively classified E60 and E90.
  • the EN 50200 standard consists of mounting and fixing by means of metal rings an electric cable in the form of a U on a plate of refractory material.
  • the electrical cable during the test is subjected to a flame (850 ° C) as well as a metal shock delivered via a metal bar which falls on the plate of refractory material every 5 minutes. Electrical conductors being under their operating voltage must not break or give rise to short circuits.
  • the electrical cable having satisfied the test for 15, 30, 60, 90 or 120 minutes is then respectively classified PH15, PH30, PH60 PH90 or PH120.
  • Table 2 shows the very satisfactory results of the fire resistance tests of insulating layers of electric cables according to the present invention.
  • the electrical cables used for said tests consist of at least two copper wires respectively insulated, all of these insulated copper son being surrounded by a conventional type of protection HFFR well known to those skilled in the art.
  • the electrically insulating layers of the copper wires of each set are respectively obtained from compositions A1 to A3, B1 to B4 and C1 to C3. ⁇ b> ⁇ u> Table 2 ⁇ / u> ⁇ /b> standards IEC 60331 part 31 EN 50200 DIN 4102 Results FE 180 PH 90 E30
  • the extruded insulation layers obtained respectively from the compositions A2, A4, A5 and A6 were subjected to a mechanical penetration resistance test.
  • the procedure consists mainly in driving a penetrating member at constant speed into each combustion residue, and simultaneously measuring, by means of a force sensor, the resistance of the burnt material as a function of the effective depth of penetration.
  • the penetrating member is concretely in the form of a cylinder 6mm in diameter and 20mm in length. In order to provide a convex contact surface, this cylinder is used in a position parallel to the outer surface of the residue to be tested, and with a direction of displacement perpendicular to said outer surface.
  • the penetration speed is set at 10mm / min.
  • the cylindrical geometry of the penetrating member makes it possible simultaneously to quantify the compressive strength and the creep resistance.
  • a Zwick / Roel Z010 ® type compression machine is used to continuously perform series of resistance measurements from which the characteristic value of the residual cohesion, ie the maximum resistance force, will be deduced each time. reached after penetrating 50% of the thickness of the sample.
  • Table 3 below collates the characteristic values of residual cohesion, denoted Fmax-50% expressed in Newton, for the insulating layers extruded after a combustion at 920 ° C. ⁇ b> ⁇ u> Table 3 ⁇ / u> ⁇ /b> Extruded insulating layers obtained from the following compositions: A2 A4 AT 5 A6 Fmax-50% after combustion at 920 ° C 231 338 125 215
  • compositions A2, A4 and A6 have excellent residual cohesion after being burned at 920 ° C.
  • the residual cohesion result (125N after combustion at 920 ° C.) corresponding to the insulating layer obtained from the composition A5 is much lower than those obtained from the insulating layers of the invention.

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  • Compositions Of Macromolecular Compounds (AREA)
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  • Inorganic Insulating Materials (AREA)

Description

La présente invention se rapporte à un câble d'énergie et/ou de télécommunication comportant au moins une couche électriquement isolante qui est en outre en mesure de résister à des conditions thermiques extrêmes.The present invention relates to an energy and / or telecommunication cable comprising at least one electrically insulating layer which is also able to withstand extreme thermal conditions.

Elle s'applique typiquement, mais non exclusivement, aux câbles de sécurité, c'est-à-dire à des câbles d'énergie ou de télécommunication destinés à rester opérationnels pendant un temps défini lorsqu'ils sont soumis à de fortes chaleurs et/ou directement au feu.It applies typically, but not exclusively, to safety cables, that is to say to energy or telecommunication cables intended to remain operational for a defined time when they are subjected to high heat and / or or directly to the fire.

Aujourd'hui, un des enjeux majeurs de l'industrie du câble est l'amélioration du comportement et des performances des câbles dans des conditions thermiques extrêmes, notamment celles rencontrées lors d'un incendie. Pour des raisons essentiellement de sécurité, il est en effet indispensable de maximiser les capacités du câble à retarder la propagation des flammes d'une part, et à résister au feu d'autre part afin d'assurer une continuité de fonctionnement.Today, one of the major challenges of the cable industry is the improvement of the behavior and performance of cables in extreme thermal conditions, especially those encountered during a fire. For reasons of safety in particular, it is indeed essential to maximize the capabilities of the cable to delay the spread of flames on the one hand, and resist fire on the other hand to ensure continuity of operation.

Un ralentissement significatif de la progression des flammes, c'est autant de temps gagné pour évacuer les lieux et/ou pour mettre en oeuvre des moyens d'extinction appropriés. En cas d'incendie, le câble doit pouvoir résister au feu afin de fonctionner le plus longtemps possible et limiter sa dégradation. Un câble de sécurité se doit en outre de ne pas être dangereux pour son environnement, c'est-à-dire de ne pas dégager de fumées toxiques et/ou trop opaques lorsqu'il est soumis à des conditions thermiques extrêmes.A significant slowdown in the progression of the flames, it is as much time gained to evacuate the places and / or to implement appropriate means of extinction. In case of fire, the cable must be able to withstand the fire in order to operate as long as possible and limit its degradation. A safety cable must also not be dangerous for its environment, that is to say, not to release toxic fumes and / or too opaque when subjected to extreme thermal conditions.

Qu'il soit électrique ou optique, destiné au transport d'énergie ou à la transmission de données, un câble est schématiquement constitué d'au moins un élément conducteur, électrique ou optique, entouré par au moins une couche électriquement isolante.Whether electrical or optical, for energy transport or data transmission, a cable is schematically constituted of at least one conductive element, electrical or optical, surrounded by at least one electrically insulating layer.

A titre d'exemple, la couche électriquement isolante peut être une isolation directement en contact avec au moins un élément conducteur du câble. Elle peut être également une gaine de protection entourant un ou plusieurs éléments conducteurs isolés.By way of example, the electrically insulating layer may be an insulation directly in contact with at least one conductive element of the cable. It can also be a protective sheath surrounding one or more insulated conductive elements.

Une composition connue de couche isolante pour câble, susceptible de résister au feu, est décrite dans le document WO 2004/035711 . Cette composition comprend un polymère organique et plusieurs charges inorganiques qui peuvent être notamment du mica, du borate de zinc, et des oxydes métalliques tels que des oxydes de calcium, de fer, de magnésium, d'aluminium, de zirconium, de zinc, d'étain ou de baryum.A known fire-resistant cable insulating layer composition is described in the document WO 2004/035711 . This composition comprises an organic polymer and several inorganic fillers which may be in particular mica, zinc borate, and metal oxides such as oxides of calcium, iron, magnesium, aluminum, zirconium, zinc, zinc tin or barium.

Toutefois, ce type de composition ne permet pas d'assurer une intégrité mécanique et électrique du câble, c'est-à-dire la poursuite de son fonctionnement de manière optimale en cas d'incendie.However, this type of composition does not ensure mechanical and electrical integrity of the cable, that is to say the continuation of its operation optimally in case of fire.

JP 2004-95373 décrit une bande isolante pour câble flexible plat présentant des propriétés de retardement à la flamme comprenant comme éléments essentiels une résine polyester et un hydroxyde métallique. JP 2004-95373 discloses an insulating strip for flat flexible cable having flame retardance properties comprising as essential elements a polyester resin and a metal hydroxide.

L'objet de la présente invention est de pallier les inconvénients des solutions de l'état de la technique en offrant notamment un câble comprenant une couche isolante présentant un compromis optimal entre ses propriétés d'isolation électrique et de tenue mécanique dans des conditions thermiques extrêmes.The object of the present invention is to overcome the drawbacks of the solutions of the state of the art by providing in particular a cable comprising an insulating layer having an optimal compromise between its electrical insulation properties and mechanical strength in extreme thermal conditions. .

La solution selon la présente invention est de proposer un câble d'énergie et/ou de télécommunication comportant au moins un élément conducteur entouré par au moins une couche isolante, notamment une couche électriquement isolante, s'étendant le long du câble, la couche isolante étant obtenue à partir d'une composition comprenant les composés suivants :

  1. a) un polymère organique,
  2. b) un composé inorganique comprenant un oxyde de potassium et/ou un de ses précurseurs,
  3. c) un oxyde de bore et/ou un de ses précurseurs, et
  4. d) de l'oxyde de calcium CaO et/ou un de ses précurseurs,
caractérisé en ce que la quantité du composé d est au moins de 10 % en poids, de préférence au moins de 20 % en poids, du poids total des composés b, c et d dans la composition.The solution according to the present invention is to propose an energy and / or telecommunication cable comprising at least one conductive element surrounded by at least one insulating layer, in particular an electrically insulating layer, extending along the cable, the insulating layer. being obtained from a composition comprising the following compounds:
  1. a) an organic polymer,
  2. b) an inorganic compound comprising a potassium oxide and / or a precursor thereof,
  3. c) a boron oxide and / or a precursor thereof, and
  4. d) calcium oxide CaO and / or one of its precursors,
characterized in that the amount of the compound d is at least 10% by weight, preferably at least 20% by weight, of the total weight of the compounds b, c and d in the composition.

Cette association de charges inorganiques (composés b, c et d) est adaptée de façon optimale pour réagir dans les conditions d'un incendie et former ainsi un composé céramique réfractaire : la couche isolante est dite céramisable.This combination of inorganic fillers (compounds b, c and d) is optimally adapted to react in the conditions of a fire and thus form a refractory ceramic compound: the insulating layer is said to be ceramizable.

Avantageusement, le câble selon la présente invention satisfait notamment aux normes IEC 60331 part 21 ou 23, DIN 4102 part 12 et EN 50200.Advantageously, the cable according to the present invention satisfies in particular the standards IEC 60331 part 21 or 23, DIN 4102 part 12 and EN 50200.

On entend par les termes « précurseur d'un oxyde métallique x» (cf. précurseur d'oxyde de potassium, d'oxyde de bore ou d'oxyde de calcium) tout élément inorganique apte à former sous l'action d'une élévation de température ledit oxyde métallique x. Notamment, ledit élément inorganique forme l'oxyde métallique à une température T inférieure à la température Tc de (début de) céramisation de la couche isolante.The terms "precursor of a metal oxide x" (precursor of potassium oxide, boron oxide or calcium oxide) are understood to mean any inorganic element capable of forming under the action of an elevation temperature said metal oxide x. In particular, said inorganic element forms the metal oxide at a temperature T lower than the temperature Tc of (beginning of) ceramization of the insulating layer.

La céramisation correspond classiquement à la consolidation par l'action de la chaleur d'un agglomérat granulaire (particules) plus ou moins compact, avec ou sans fusion d'un des constituants. Elle comprend typiquement trois étapes successives, à savoir :

  1. i. le réarrangement et le collage des particules,
  2. ii. la densification et l'élimination des porosités intergranulaires, et
  3. iii. le grossissement des grains et l'élimination progressive des porosités fermées.
Ceramization conventionally corresponds to the consolidation by the action of heat of a granular agglomerate (particles) more or less compact, with or without fusion of one of the constituents. It typically comprises three successive steps, namely:
  1. i. rearrangement and bonding of particles,
  2. ii. densification and elimination of intergranular porosities, and
  3. iii. grain enlargement and gradual elimination of closed porosities.

La température de début de céramisation est considérée comme étant la température suffisante pour observer le réarrangement et le collage des particules énoncées à l'étape i ci-dessus.The ceramization start temperature is considered to be the temperature sufficient to observe the rearrangement and sticking of the particles set forth in step i above.

Composé aCompound a

La nature du polymère organique de la composition selon la présente invention n'est nullement limitative.The nature of the organic polymer of the composition according to the present invention is in no way limiting.

Ce peut être tout type de polymère organique bien connu de l'homme du métier, notamment apte à pouvoir être extrudé, du type polymère thermoplastique ou élastomère.It can be any type of organic polymer well known to those skilled in the art, especially capable of being extruded, of the thermoplastic or elastomeric polymer type.

Bien entendu, le polymère organique peut être un mélange de plusieurs polymères organiques, ou peut être un mélange de polymères constitué d'au moins un polymère organique majoritaire dans le mélange et d'au moins un autre polymère de nature différente.Of course, the organic polymer may be a mixture of several organic polymers, or may be a mixture of polymers consisting of at least one major organic polymer in the mixture and at least one other polymer of different nature.

Le polymère organique est de préférence choisi parmi un polymère d'oléfine, un polymère d'acrylate ou méthacrylate, un polymère de vinyle, et un polymère fluoré, ou un de leurs mélanges.The organic polymer is preferably selected from an olefin polymer, an acrylate or methacrylate polymer, a vinyl polymer, and a fluoropolymer, or a mixture thereof.

Le polymère d'oléfine est notamment choisi parmi un homopolymère ou copolymère d'éthylène, et un homopolymère ou copolymère de propylène, ou un de leurs mélanges.The olefin polymer is especially chosen from a homopolymer or copolymer of ethylene, and a homopolymer or copolymer of propylene, or a mixture thereof.

A titre d'exemple préféré, le polymère d'oléfine est choisi parmi un homopolymère d'éthylène, un copolymère d'éthylène-octène (PEO), un copolymère d'éthylène et d'acétate de vinyle (EVA), un copolymère d'éthyle propylène diène monomère (EPDM), un copolymère d'éthylène et d'acrylate de méthyle (EMA), un copolymère d'éthylène et d'acrylate de butyle (EBA), et un copolymère d'éthylène et d'acrylate d'éthyle (EEA), ou un de leurs mélanges.By way of preferred example, the olefin polymer is chosen from an ethylene homopolymer, an ethylene-octene (PEO) copolymer, an ethylene-vinyl acetate (EVA) copolymer, a copolymer of propylene diene monomer (EPDM), a copolymer of ethylene and methyl acrylate (EMA), a copolymer of ethylene and butyl acrylate (EBA), and a copolymer of ethylene and acrylate ethyl (EEA), or a mixture thereof.

Composé bCompound b

Le composé b peut être avantageusement un oxyde de potassium en tant que tel ou un phyllosilicate comprenant un oxyde de potassium. Plus particulièrement, le phyllosilicate comprenant un oxyde de potassium est préférentiellement un phyllosilicate d'aluminium comprenant un oxyde de potassium.The compound b may advantageously be a potassium oxide as such or a phyllosilicate comprising a potassium oxide. More particularly, the phyllosilicate comprising a potassium oxide is preferably an aluminum phyllosilicate comprising a potassium oxide.

L'oxyde de potassium a de préférence la formule chimique suivante : K2O. D'autres types d'oxydes de potassium tels que par exemple des oxydes complexes, ou en d'autres termes des polyoxométallates, peuvent être également considérés dans le cadre de l'invention.The potassium oxide preferably has the following chemical formula: K 2 O. Other types of potassium oxides such as, for example, complex oxides, or in other words polyoxometalates, can also be considered in the context of the present invention. of the invention.

Les phyllosilicates comprenant un oxyde de potassium peuvent être certains types de mica tels que les micas aluminoceladonite, boromuscovite, celadonite, chromphyllite, ferro-aluminoceladonite, ferrocelatonite, muscovite, roscoelite, annite, biotite, eastonite, hendricksite, lepidolite, masutomilite, montdorite, norrishite, polylithionite, phlogopite, siderophyllite, tainiotite, tetra-ferri-annite, tetra-ferriphlogopite, trilithionite, zinnwaldite, anadite, glauconite, ou illite.The phyllosilicates comprising a potassium oxide may be certain types of mica such as micas aluminoceladonite, boromuscovite, celadonite, chromphyllite, ferroaluminoceladonite, ferrocelatonite, muscovite, roscoelite, annite, biotite, eastonite, hendricksite, lepidolite, masutomilite, montdorite, norrishite , polylithionite, phlogopite, siderophyllite, tainiotite, tetra-ferri-annite, tetra-ferriphlogopite, trilithionite, zinnwaldite, anadite, glauconite, or illite.

On préférera les phyllosilicates d'aluminium comprenant un oxyde de potassium tels que les micas aluminoceladonite, chromphyllite, ferro-aluminoceladonite, muscovite, roscoelite, annite, biotite, eastonite, hendricksite, lepidolite, masutomilite, montdorite, polylithionite, phlogopite, siderophyllite, trilithionite, zinnwaldite, anadite, glauconite, ou illite.Aluminum phyllosilicates comprising a potassium oxide such as micas aluminoceladonite, chromphyllite, ferroaluminoceladonite, muscovite, roscoelite, annite, biotite, eastonite, hendricksite, lepidolite, masutomilite, montdorite, polylithionite, phlogopite, siderophyllite, trilithionite, are preferred. zinnwaldite, anadite, glauconite, or illite.

Dans les phyllosilicates d'aluminium comprenant un oxyde de potassium, on préférera le mica muscovite de formule chimique 6SiO2-3AbO3-K2O-2H2O ou le mica phlogopite de formule chimique 6SiO2-AbO3-K2O-6MgO-2H2O.In aluminum phyllosilicates comprising a potassium oxide, the muscovite mica of the chemical formula 6SiO 2 -3AbO 3 -K 2 O-2H 2 O or the phlogopite mica of the chemical formula 6SiO 2 -AbO 3 -K 2 O- 6MgO-2H 2 O.

La quantité du composé b peut être au moins de 2 parties en poids, de préférence au moins de 3 parties en poids, et encore plus préférentiellement au moins de 6 parties en poids, pour 100 parties en poids de polymère(s) dans la composition.The amount of the compound b may be at least 2 parts by weight, preferably at least 3 parts by weight, and still more preferably at least 6 parts by weight, per 100 parts by weight of polymer (s) in the composition .

Par ailleurs, la quantité du composé b peut être au moins de 2% en poids, de préférence au moins de 5% en poids, et encore plus préférentiellement au moins de 10% en poids, du poids total des composés b, c et d dans la composition.Furthermore, the amount of the compound b may be at least 2% by weight, preferably at least 5% by weight, and still more preferably at least 10% by weight, of the total weight of the compounds b, c and d in the composition.

Composé cCompound c

L'oxyde de bore peut avoir typiquement la formule suivante : B2O3. Toutefois, B2O3 n'existe pas sous cette forme à l'état libre. De ce fait, on utilise généralement un précurseur d'oxyde de bore.The boron oxide may typically have the following formula: B 2 O 3 . However, B 2 O 3 does not exist in this form in the free state. As a result, a boron oxide precursor is generally used.

Le précurseur d'oxyde de bore peut être choisi par exemple parmi le borate de zinc, le phosphate de bore, l'acide borique, le borate de calcium (e.g. la colémanite de formule chimique Ca2B6O11,5H2O) et le borate de sodium (e.g. le borax de formule chimique Na2B4O7,10H2O).The precursor of boron oxide may be chosen for example from zinc borate, boron phosphate, boric acid, calcium borate (eg colemanite of chemical formula Ca 2 B 6 O 11 , 5H 2 O) and sodium borate (eg borax of the chemical formula Na 2 B 4 O 7 , 10H 2 O).

Le précurseur d'oxyde de bore est de préférence déshydraté, notamment lorsque ledit précurseur est le borate de zinc, afin d'éviter la déshydratation dudit précurseur lorsque la couche isolante est soumise au feu et ainsi perturber la stabilité dimensionnelle de la céramique formée.The boron oxide precursor is preferably dehydrated, especially when said precursor is zinc borate, in order to avoid dehydration of said precursor when the insulating layer is subjected to fire and thus to disturb the dimensional stability of the ceramic formed.

La quantité du composé c peut être au moins de 20 parties en poids, et de préférence au moins de 25 parties en poids, pour 100 parties en poids de polymère(s) dans la composition.The amount of compound c may be at least 20 parts by weight, and preferably at least 25 parts by weight, per 100 parts by weight of polymer (s) in the composition.

Par ailleurs, la quantité du composé c peut être au moins de 10 % en poids, de préférence au moins de 15 % en poids, et plus préférentiellement au moins de 20 % en poids, du poids total des composés b, c et d dans la composition.Furthermore, the amount of compound c may be at least 10% by weight, preferably at least 15% by weight, and more preferably at least 20% by weight, of the total weight of compounds b, c and d in the composition.

Composé dComposed of

Un des précurseurs d'oxyde de calcium CaO peut être le carbonate de calcium. Entre l'oxyde de calcium, un précurseur d'oxyde de calcium et le mélange oxyde de calcium et précurseur d'oxyde de calcium, l'oxyde de calcium en tant que tel est préféré.One of the calcium oxide precursors CaO may be calcium carbonate. Between calcium oxide, a calcium oxide precursor and the calcium oxide and calcium oxide precursor mixture, calcium oxide as such is preferred.

La quantité du composé d peut être avantageusement au moins de 10 parties en poids, de préférence au moins de 20 parties en poids, et encore plus préférentiellement au moins de 25 parties en poids, pour 100 parties en poids de polymère(s) dans la composition.The amount of the compound d may advantageously be at least 10 parts by weight, preferably at least 20 parts by weight, and still more preferably at least 25 parts by weight, per 100 parts by weight of polymer (s) in the composition.

Par ailleurs, la quantité du composé d peut être, quant à elle, avantageusement au moins de 15 % en poids, et de préférence au moins de 20 % en poids, du poids total des composés b, c et d dans la composition.Moreover, the amount of the compound d can advantageously be at least 15% by weight, and preferably at least 20% by weight, of the total weight of the compounds b, c and d in the composition.

Mode de réalisation particulier : le composé b est du micaParticular embodiment: compound b is mica

L'oxyde de potassium est présent dans certains types de mica comme mentionné ci-avant. Lors de l'utilisation de mica en tant que composé b, la quantité du composé b peut être au moins de 40 % en poids, du poids total des composés b, c et d dans la composition.Potassium oxide is present in some types of mica as mentioned above. When using mica as compound b, the amount of compound b can be at least 40% by weight, the total weight of compounds b, c and d in the composition.

De préférence, la composition peut comprendre une quantité du composé b au plus de 80 % en poids, une quantité du composé c au plus de 30 % en poids, et une quantité du composé d au plus de 50 % en poids, lesdites quantités étant définies par rapport au poids total des composés b, c et d dans la composition.Preferably, the composition may comprise an amount of compound b at most 80% by weight, an amount of compound c at most 30% by weight, and an amount of the compound of at most 50% by weight, said amounts being defined with respect to the total weight of compounds b, c and d in the composition.

Pour résumé, et selon ce mode de réalisation, la composition peut ainsi comprendre une quantité du composé b de 40 à 80 % en poids, une quantité du composé c de 10 à 30 % en poids, et une quantité du composé d de 10 à 50 % en poids, lesdites quantités étant définies par rapport au poids total des composés b, c et d dans la composition.For summary, and according to this embodiment, the composition can thus comprise an amount of compound b of 40 to 80% by weight, an amount of compound c of 10 to 30% by weight, and an amount of compound d of 10 to 50% by weight, said amounts being defined relative to the total weight of compounds b, c and d in the composition.

Selon un exemple préféré de réalisation, la composition comprend une quantité du composé b de 60 % en poids, une quantité du composé c de 20 % en poids, et une quantité du composé d de 20 % en poids, lesdites quantités étant définies par rapport au poids total des composés b, c et d dans la composition.According to a preferred embodiment, the composition comprises an amount of the compound b of 60% by weight, a quantity of the compound c of 20% by weight, and a quantity of the compound d of 20% by weight, said amounts being defined in relation to the total weight of compounds b, c and d in the composition.

Autres charges inorganiquesOther inorganic fillers

La composition selon la présente invention peut comprendre en outre d'autres charges inorganiques du type nanoparticules.The composition according to the present invention may furthermore comprise other inorganic fillers of the nanoparticle type.

Lesdites nanoparticules ont typiquement au moins l'une de leurs dimensions de taille nanométrique (10-9 mètre). Plus particulièrement, la dimension moyenne des nanoparticules minérales est d'au plus 400 nm, de préférence d'au plus 300 nm, et plus préférentiellement d'au plus 100 nm.Said nanoparticles typically have at least one of their nanometric dimensions (10 -9 meters). More particularly, the average size of the mineral nanoparticles is at most 400 nm, preferably at most 300 nm, and more preferably at most 100 nm.

La dimension moyenne des nanoparticules est classiquement déterminée par des méthodes bien connues de l'homme du métier comme par exemple par granulométrie laser ou par des techniques de microscopies, notamment par MEB (Microscopie Electronique à Balayage) ou MET (Microscopie Electronique en Transmission).The average size of the nanoparticles is conventionally determined by methods that are well known to those skilled in the art, for example by laser granulometry or by microscopy techniques, in particular by SEM (Scanning Electron Microscopy) or TEM (Transmission Electron Microscopy).

Ces nanoparticules ont de préférence un facteur de forme d'au moins 100, le facteur de forme étant le rapport de la plus grande dimension d'une nanoparticule minérale sur la plus petite dimension de ladite nanoparticule.These nanoparticles preferably have a form factor of at least 100, the form factor being the ratio of the largest dimension of a mineral nanoparticle to the smallest dimension of said nanoparticle.

De préférence, les nanoparticules sont des phyllosilicates choisis notamment parmi les montmorillonites, les sépiolites, les illites, les attapulgites, les talcs, et les kaolins, ou un de leurs mélanges.Preferably, the nanoparticles are phyllosilicates chosen in particular from montmorillonites, sepiolites, illites, attapulgites, talcs, and kaolins, or a mixture thereof.

Afin de garantir une couche isolante dite HFFR (pour l'anglicisme « Hologen Free Flame Retardant »), la composition ne comprend pas de charges inorganiques halogénées. La composition peut en outre ne pas comprendre de polymères halogénés tels que par exemple des polymères fluorés ou des polymères chlorés tels que le polychlorure de vinyle (PVC).In order to guarantee a so-called HFFR ( Hologen Free Flame Retardant ) insulating layer, the composition does not comprise halogenated inorganic fillers. The composition may furthermore not include halogenated polymers such as, for example, fluorinated polymers or chlorinated polymers such as polyvinyl chloride (PVC).

Les quantités de charges inorganiques dans la composition (composés b, c et d, ainsi qu'optionnellement d'autres charges inorganiques) peuvent être définies en ce que la composition comprend au moins 20 parties en poids, de préférence au moins 40 parties en poids, de préférence au moins 60 parties en poids, et encore plus préférentiellement au moins 90 parties en poids de charges inorganiques, pour 100 parties en poids de polymère(s).The amounts of inorganic fillers in the composition (compounds b, c and d, as well as optionally other inorganic fillers) can be defined in that the composition comprises at least 20 parts by weight, preferably at least 40 parts by weight preferably at least 60 parts by weight, and even more preferably at least 90 parts by weight of inorganic fillers, per 100 parts by weight of polymer (s).

La limite inférieure de 90 parties en poids est notamment prise en compte lorsque le composé b est du mica (i.e. phyllosilicate comprenant un oxyde de potassium).The lower limit of 90 parts by weight is especially taken into account when the compound b is mica (i.e. phyllosilicate comprising a potassium oxide).

De préférence, la composition comprend au plus 200 parties en poids de charges inorganiques pour 100 parties en poids de polymère(s), afin de limiter les problèmes de rhéologies dans la composition.Preferably, the composition comprises at most 200 parts by weight of inorganic fillers per 100 parts by weight of polymer (s), in order to limit the problems of rheologies in the composition.

Selon une particularité de la présente invention, la composition peut être réticulée afin d'obtenir une couche isolante réticulée. La réticulation de la composition peut s'effectuer par les techniques classiques de réticulation bien connues de l'homme du métier telles que par exemple la réticulation silane en présence d'un agent de réticulation, la réticulation peroxyde sous l'action de la chaleur, ou la réticulation par voie photochimique telle que l'irradiation sous rayonnement béta, ou irradiation sous rayonnement ultraviolet en présence d'un photoamorceur.According to a feature of the present invention, the composition may be crosslinked to obtain a crosslinked insulating layer. The crosslinking of the composition can be carried out by conventional crosslinking techniques well known to those skilled in the art such as, for example, silane crosslinking in the presence of a crosslinking agent, peroxide crosslinking under the action of heat, or photochemically cross-linking such as irradiation with beta radiation, or irradiation with ultraviolet radiation in the presence of a photoinitiator.

D'autres caractéristiques et avantages de la présente invention apparaîtront à la lumière des exemples qui vont suivre en référence aux figures annotées, lesdits exemples et figures étant donnés à titre illustratif et nullement limitatif.

  • La figure 1 représente de manière schématique une perspective en coupe d'un câble électrique ayant au moins une couche isolante conforme à l'invention.
  • La figure 2 représente de manière schématique une perspective en coupe d'un autre câble électrique ayant au moins une couche isolante conforme à l'invention.
Other features and advantages of the present invention will appear in light of the examples which follow with reference to the annotated figures, said examples and figures being given for illustrative and not limiting.
  • The figure 1 schematically represents a sectional perspective of an electric cable having at least one insulating layer according to the invention.
  • The figure 2 schematically represents a sectional perspective of another electrical cable having at least one insulating layer according to 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.

Dans un premier exemple de réalisation, la figure 1 représente un câble électrique 1 comprenant un élément conducteur 2 de type massif, entouré par une couche isolante du type isolation 3 directement en contact avec l'élément conducteur, cette dernière étant elle-même entourée par une couche isolante du type gaine de protection 4.In a first embodiment, the figure 1 represents an electric cable 1 comprising a solid-type conducting element 2, surrounded by an insulating-type insulating layer 3 directly in contact with the conductive element, the latter being itself surrounded by an insulating layer of the protective sheath type 4.

Dans un second exemple de réalisation, la figure 2 représente également un câble électrique 10 comprenant au moins deux éléments conducteurs 12 de type multibrin. Chaque multibrin 12 est entouré par une couche isolante du type isolation 13 directement en contact avec l'élément conducteur, l'ensemble de ces multibrins isolés étant entouré par une couche isolante du type gaine de protection 14.In a second embodiment, the figure 2 also represents an electrical cable 10 comprising at least two conductive elements 12 of multi-strand type. Each strand 12 is surrounded by an insulation insulating layer 13 directly in contact with the conductive element, all of these isolated strands being surrounded by an insulating layer of the protective sheath type 14.

Que ce soit dans la figure 1 ou 2, la couche isolante 3, 13 et/ou la gaine de protection 4, 14 peuvent être obtenue(s) à partir de la composition selon la présente invention.Whether in the figure 1 or 2 the insulating layer 3, 13 and / or the protective sheath 4, 14 can be obtained from the composition according to the present invention.

Typiquement, l'isolation 3, 13 a une épaisseur de 0,6 à 2,4 mm et la gaine de protection 4, 14 a une épaisseur de 1 à 2,5 mm.Typically, the insulation 3, 13 has a thickness of 0.6 to 2.4 mm and the protective sheath 4, 14 has a thickness of 1 to 2.5 mm.

La composition selon l'invention est classiquement mise en forme par extrusion autour de ou des éléments conducteurs pour former l'isolation 3, 13 et/ou la gaine de protection 4, 14.The composition according to the invention is conventionally shaped by extrusion around or conductive elements to form the insulation 3, 13 and / or the protective sheath 4, 14.

L'extrusion de ladite composition peut être une extrusion dite en compression ou bourrante, ou une extrusion dite tubante.The extrusion of said composition may be an extrusion said compression or stuffing, or a so-called tubing extrusion.

L'extrusion tubante permet d'obtenir une couche isolante tubante, c'est-à-dire une couche en forme de tube d'une certaine épaisseur dont la surface interne et la surface externe sont respectivement deux cylindres sensiblement concentriques.The tubular extrusion makes it possible to obtain a tubular insulating layer, that is to say a tube-shaped layer of a certain thickness whose inner surface and the outer surface are respectively two substantially concentric cylinders.

Ainsi, la couche isolante tubante ne remplit pas les interstices entre les éléments conducteurs (isolés ou non) et ménage ainsi des espaces vides entre elle et les éléments conducteurs isolés ou non qu'elle entoure, notamment les espaces vides occupent au moins 10% de la section du câble.Thus, the tubular insulating layer does not fill the interstices between the conductive elements (isolated or not) and thus provides empty spaces between it and the insulated or insulated conductive elements that it surrounds, especially the empty spaces occupy at least 10% of the section of the cable.

Dans certains modes de réalisation, la couche isolante laisse les éléments conducteurs libres à l'intérieur de ladite couche.In some embodiments, the insulating layer leaves the free conductive elements within said layer.

L'extrusion bourrante permet d'obtenir une couche bourrante, c'est-à-dire une couche remplissant les interstices entre les éléments conducteurs (isolés ou non) dont les volumes sont accessibles, et ainsi ladite couche est directement en contact avec les éléments conducteurs isolés ou non.The stuffing extrusion makes it possible to obtain a stuffing layer, that is to say a layer filling the interstices between the conductive elements (isolated or not) whose volumes are accessible, and thus said layer is directly in contact with the elements isolated conductors or not.

ExemplesExamples

Différentes couches isolantes selon la présente invention et selon l'art antérieur ont été préparées afin de montrer le maintient de l'intégrité électrique desdits couches pendant des essais de résistances au feu.Different insulating layers according to the present invention and according to the prior art have been prepared in order to show the maintenance of the electrical integrity of said layers during fire resistance tests.

Pour ce faire, les tableaux 1a et 1b ci-après détaillent les compositions mise en oeuvre pour obtenir lesdites couches isolantes.To do this, Tables 1a and 1b below detail the compositions used to obtain said insulating layers.

Il est à noter que les quantités mentionnées dans les tableaux 1a et 1b sont classiquement exprimées en parties en poids pour cent parties en poids de polymère(s) (pcr). Tableau 1a Compositions A1 A2 A3 B1 B2 B3 B4 C1 C2 C3 EVA 28 100 / 20 / / / / 50 57,5 / EVA 28 greffé silane 1,5% / / / / / 30 30 / / / EVA 40 greffé silane 1,5% / / / / / 70 70 / / / PEO / 100 70 / / / / / / 55 PEO greffé silane 1,2% / / / 50 / 1 / / / / PEO greffé silane 2% / / / / 100 / / / / / EPDM / / / / / / / 50 37,5 25 EPDM greffé silane z / / / 50 / / / / / / EVA greffé AM / / / / / / / / 5 / LLDPE greffé AM / / 10 / / / / / / / EMA / / / / / / / / / 20 Borate de zinc 30 30 26 30 30 30 25 30 30 30 Mica 1 90 90 78 90 90 90 75 90 90 90 Oxyde de calcium 30 30 26 30 30 30 25 30 30 30 Phyllosilicates 100 / / 20 20 / / / 20 20 20 Peroxyde / / / / / / / 6 6 4,5 Tableau 1b Compositions A4 A5 A6 PEO 100 100 100 Borate de zinc 30 30 30 Mica 2 90 / / Phyllosilicate 1 / 90 / Phyllosilicate 2 / / 90 Oxyde de calcium 30 30 30 It should be noted that the amounts mentioned in Tables 1a and 1b are conventionally expressed in parts by weight per hundred parts by weight of polymer (s) (pcr). <b><u> Table 1a </ u></b> compositions A1 A2 A3 B1 B2 B3 B4 C1 C2 C3 EVA 28 100 / 20 / / / / 50 57.5 / EVA 28 silane graft 1.5% / / / / / 30 30 / / / EVA 40 grafted silane 1.5% / / / / / 70 70 / / / PEO / 100 70 / / / / / / 55 PEO grafted silane 1.2% / / / 50 / 1 / / / / PEO grafted silane 2% / / / / 100 / / / / / EPDM / / / / / / / 50 37.5 25 EPDM grafted silane z / / / 50 / / / / / / AM grafted EVA / / / / / / / / 5 / LLDPE grafted AM / / 10 / / / / / / / EMA / / / / / / / / / 20 Zinc Borate 30 30 26 30 30 30 25 30 30 30 Mica 1 90 90 78 90 90 90 75 90 90 90 Calcium oxide 30 30 26 30 30 30 25 30 30 30 Phyllosilicates 100 / / 20 20 / / / 20 20 20 Peroxide / / / / / / / 6 6 4.5 compositions A4 AT 5 A6 PEO 100 100 100 Zinc Borate 30 30 30 Mica 2 90 / / Phyllosilicate 1 / 90 / Phyllosilicate 2 / / 90 Calcium oxide 30 30 30

L'origine des différents constituants des tableaux 1a et 1b est la suivante :

  • EVA 28 est un copolymère d'éthylène vinyle acétate comprenant 28 % de groupements d'acétate de vinyle, commercialisé par la société Arkema sous la référence Evatane 2803 ;
  • EVA 28 greffé silane 1,5% est un copolymère d'éthylène vinyle acétate comprenant 28 % de groupements d'acétate de vinyle, commercialisé par la société Arkema sous la référence Evatane 2803, ce copolymère ayant ensuite été greffé silane avec 1,5 % d'un agent de réticulation silane (voir détails ci-après) ;
  • EVA 40 greffé silane 1,5% est un copolymère d'éthylène vinyle acétate comprenant 40 % de groupements d'acétate de vinyle, commercialisé par la société Arkema sous la référence Evatane 2803, ce copolymère ayant ensuite été greffé silane avec 1,5 % d'un agent de réticulation silane (voir détails ci-après) ;
  • PEO est un copolymère d'éthylène-octène commercialisé par la société Dow sous la référence Engage 8003 ;
  • PEO greffé silane 1,2% est un copolymère d'éthylène-octène commercialisé par la société Dow sous la référence Engage 8003, ce copolymère ayant ensuite été greffé silane avec 1,2 % d'un agent de réticulation silane (voir détails ci-après) ;
  • PEO greffé silane 2% est un copolymère d'éthylène-octène commercialisé par la société Dow sous la référence Engage 8003, ce copolymère ayant ensuite été greffé silane avec 2 % d'un agent de réticulation silane (voir détails ci-après) ;
  • EPDM est un copolymère d'éthylène propylène diène monomère commercialisé par la société Dow sous la référence Nordel 4725 ;
  • EPDM greffé silane 1,5% est un copolymère d'éthylène propylène diène monomère commercialisé par la société Dow sous la référence Nordel 4725, ce copolymère ayant ensuite été greffé silane avec 1,5 % d'un agent de réticulation silane (voir détails ci-après) ;
  • EVA greffé AM est un copolymère d'éthylène vinyle acétate greffé anhydride maléique commercialisé par la société Arkema sous la référence Orevac 18211 ;
  • LLDPE greffé AM est un homopolymère d'éthylène linéaire de basse densité greffé anhydride maléique commercialisé par la société Arkema sous la référence Orevac 18302 ;
  • EMA est un copolymère d'éthylène et d'acrylate de méthyle commercialisé par la société Arkema sous la référence Lotryl 24 MA 005 ;
  • Borate de zinc est du borate de zinc déshydraté commercialisé par la société Rio Tinto Minerals sous la référence Fire brake 500 ;
  • Mica 1 est du mica de type muscovite commercialisé par la société Microfine sous la référence Mica sx300 ; Mica 1 comprend de 7 à 10% en poids de K2O ;
  • Mica 2 est du mica commercialisé par la société Imerys sous la référence Mica Mu M2/1 ; Mica 2 comprend environ 8,5% en poids de K2O ;
  • Phyllosilicate 1 est de la kaolinite commercialisée par la société Imerys sous la référence Argirec B24 ; Phyllosilicate 1 ne comprend pas de K2O ;
  • Phyllosilicate 2 est des phyllosilicates d'aluminium commercialisés par la société Imerys sous la référence Hexafil ; Phyllosilicate 2 comprend de 2,3 à 3,2% en poids de K2O ;
  • Oxyde de calcium est de l'oxyde de calcium CaO commercialisé par la société Omya sous la référence Caloxol PG ;
  • Phyllosilicates 100 sont des nanoparticules de Montmorillonite, commercialisées par la société Rockwood sous la référence Nanofil 5 ; Phyllosilicates 100 ne comprend pas d'oxyde de potassium ;
  • Peroxyde est du peroxyde de dicumyle commercialisé par la société Akzo Nobel sous la référence Perkadox BC40 (peroxyde de dicumyle) ou Perkadox 14/40 (1.3 bis (t- butyle peroxyisopropyl) benzène).
The origin of the different constituents of Tables 1a and 1b is as follows:
  • EVA 28 is a copolymer of ethylene vinyl acetate comprising 28% of vinyl acetate groups, sold by Arkema under the reference Evatane 2803;
  • EVA 28 grafted silane 1.5% is a copolymer of ethylene vinyl acetate comprising 28% of vinyl acetate groups, sold by Arkema under the reference Evatane 2803, this copolymer having then been grafted silane with 1.5% a silane crosslinking agent (see details below);
  • 1.5% silane grafted EVA 40 is a copolymer of ethylene vinyl acetate comprising 40% of vinyl acetate groups, sold by Arkema under the reference Evatane 2803, this copolymer having then been grafted silane with 1.5% a silane crosslinking agent (see details below);
  • PEO is an ethylene-octene copolymer marketed by Dow under the reference Engage 8003;
  • 1.2% silane grafted PEO is an ethylene-octene copolymer sold by Dow under the name Engage 8003, this copolymer having then been grafted silane with 1.2% of a silane crosslinking agent (see details below). after);
  • Silane-grafted PEO 2% is an ethylene-octene copolymer marketed by Dow under the name Engage 8003, this copolymer having then been grafted silane with 2% of a silane crosslinking agent (see details below);
  • EPDM is a copolymer of ethylene propylene diene monomer marketed by Dow under the reference Nordel 4725;
  • 1.5% silane grafted EPDM is a copolymer of ethylene propylene diene monomer marketed by Dow under the reference Nordel 4725, this copolymer having then been grafted silane with 1.5% of a silane crosslinking agent (see details below). -after);
  • AM grafted EVA is a maleic anhydride grafted ethylene vinyl acetate copolymer sold by Arkema under the reference Orevac 18211;
  • AM grafted LLDPE is a linear low density ethylene homopolymer grafted maleic anhydride marketed by Arkema under the reference Orevac 18302;
  • EMA is a copolymer of ethylene and methyl acrylate marketed by Arkema under the reference Lotryl 24 MA 005;
  • Zinc borate is dehydrated zinc borate marketed by Rio Tinto Minerals under the reference Fire brake 500;
  • Mica 1 is muscovite-type mica marketed by Microfine under the reference Mica sx300; Mica 1 comprises from 7 to 10% by weight of K 2 O;
  • Mica 2 is mica marketed by Imerys under the reference Mica Mu M2 / 1; Mica 2 comprises about 8.5% by weight of K 2 O;
  • Phyllosilicate 1 is kaolinite marketed by Imerys under the reference Argirec B24; Phyllosilicate 1 does not include K 2 O;
  • Phyllosilicate 2 is aluminum phyllosilicates marketed by Imerys under the reference Hexafil; Phyllosilicate 2 comprises from 2.3 to 3.2% by weight of K 2 O;
  • Calcium oxide is calcium oxide CaO marketed by Omya under the reference Caloxol PG;
  • Phyllosilicates 100 are nanoparticles of Montmorillonite, marketed by Rockwood under the reference Nanofil 5; Phyllosilicates 100 does not include potassium oxide;
  • Peroxide is dicumyl peroxide sold by Akzo Nobel under the reference Perkadox BC40 (dicumyl peroxide) or Perkadox 14/40 (1.3 bis (t-butyl peroxyisopropyl) benzene).

La composition peut typiquement comprendre en outre des additifs en une quantité de 5 à 20 pcr. Les additifs sont bien connus de l'homme du métier et peuvent être par exemple choisis parmi des agents de protection (antioxydants, des anti-UV, anti-cuivre), des agents de mise en oeuvre (plastifiants ou lubrifiants), et des pigments.The composition may typically further comprise additives in an amount of from 5 to 20 phr. The additives are well known to those skilled in the art and may be chosen for example from protection agents (antioxidants, anti-UV, anti-copper), processing agents (plasticizers or lubricants), and pigments .

Préparation de couches isolantes à partir des compositions A1 à A6 des tableaux 1a et 1bPreparation of insulating layers from compositions A1 to A6 of Tables 1a and 1b

On mélange en continu et en chauffant le ou les polymères à l'état fondu aux différentes charges inorganiques détaillées dans les tableaux 1a et 1 b.The melt polymer (s) is continuously blended with the various inorganic fillers detailed in Tables 1a and 1b.

Le mélange est effectué à l'aide d'un mélangeur monovis Buss ou d'une extrudeuse bivis et les charges inorganiques sont ajoutés au(x) polymère(s) à l'aide d'une trémie doseuse classique.The mixing is carried out using a Buss single-screw mixer or a twin-screw extruder and the inorganic fillers are added to the polymer (s) using a conventional metering hopper.

Le mélange du ou des polymères chargés est extrudé directement sur un fil de cuivre massif ou multibrin d'une section de 1,5 mm2, la couche isolante extrudée ayant une épaisseur de 0,8 mm.The mixture of the charged polymer (s) is extruded directly onto a solid or multi-stranded copper wire with a cross-section of 1.5 mm 2 , the extruded insulating layer having a thickness of 0.8 mm.

Préparation de couches isolantes à partir des compositions B1, B2, B3 et B4 du tableau 1aPreparation of insulating layers from compositions B1, B2, B3 and B4 of Table 1a

Dans une première étape, on mélange en continu et en chauffant les polymères du tableau 1a à l'état fondu avec un agent de réticulation silane du type alkoxysilane ou carboxysilane ensemble avec un peroxyde organique, à l'aide d'un mélangeur monovis Buss ou d'une extrudeuse bivis.In a first step, the polymers of Table 1a in the molten state are continuously mixed and heated with a silane crosslinking agent of the alkoxysilane or carboxysilane type together with an organic peroxide, using a Buss single-screw mixer or of a twin-screw extruder.

L'agent de réticulation est ajouté en une quantité de 1 à 2,5 % et celui utilisé dans les compositions B1 à B4 est le Silfin 59 commercialisé par la société Evonik.The crosslinking agent is added in an amount of 1 to 2.5% and that used in the compositions B1 to B4 is Silfin 59 sold by the company Evonik.

La température du mélange de cette première étape est telle qu'elle permet typiquement de mettre en oeuvre le mélange de polymères tout en décomposant le peroxyde organique.The temperature of the mixture of this first step is such that it typically allows the polymer mixture to be used while decomposing the organic peroxide.

Cette première étape permet d'obtenir un mélange de polymères greffé silane sous forme de granulés.This first step makes it possible to obtain a mixture of silane graft polymers in the form of granules.

Dans une deuxième étape, on mélange en continu et en chauffant le polymère greffé silane à l'état fondu aux différentes charges inorganiques détaillées dans le tableau 1a.In a second step, the molar silane graft polymer is continuously blended and heated to the various inorganic fillers detailed in Table 1a.

Le mélange est effectué à l'aide d'un autre mélangeur monovis Buss ou d'une autre extrudeuse bivis et les charges inorganiques sont ajoutées au polymère greffé silane à l'aide d'une trémie doseuse classique.Mixing is performed using another Buss single screw mixer or other twin screw extruder and the inorganic fillers are added to the silane graft polymer using a conventional metering hopper.

Cette deuxième étape permet d'obtenir un polymère greffé silane chargé, le polymère greffé silane chargé étant typiquement obtenu sous forme de granulés.This second step makes it possible to obtain a grafted silane graft polymer, the charged silane graft polymer being typically obtained in the form of granules.

Dans une troisième étape, les granulés de polymère greffé silane chargé sont mis en oeuvre à l'état fondu dans une extrudeuse monovis en présence d'un catalyseur de la réaction de condensation de groupements silanols, tel que par exemple le dibutyl dilaurate d'étain (DBTL) bien connu de l'homme du métier.In a third step, the granules of charged silane graft polymer are used in the molten state in a single-screw extruder in the presence of a catalyst for the condensation reaction of silanol groups, such as, for example, dibutyltin dilaurate. (DBTL) well known to those skilled in the art.

Le catalyseur est typiquement ajouté au polymère greffé silane chargé sous forme d'un mélange maître à base d'une polyoléfine compatible avec ledit polymère greffé.The catalyst is typically added to the charged silane graft polymer in the form of a masterbatch based on a polyolefin compatible with said graft polymer.

A titre d'exemple, le mélange maître contenant ledit catalyseur est ajouté en une quantité d'environ 2 % en poids au polymère greffé silane chargé.By way of example, the masterbatch containing said catalyst is added in an amount of about 2% by weight to the loaded silane graft polymer.

Le mélange du polymère greffé silane chargé et du catalyseur de condensation des silanols est extrudé directement sur un fil de cuivre multibrin d'une section de 1,5 mm2, la couche isolante extrudée ayant une épaisseur de 0,8 mm.The mixture of the charged silane graft polymer and the silanol condensation catalyst is extruded directly onto a 1.5 mm 2 multi-stranded copper wire, the extruded insulating layer having a thickness of 0.8 mm.

Préparation de couches isolantes à partir des compositions C1, C2 et C3 du tableau 1aPreparation of insulating layers from compositions C1, C2 and C3 of Table 1a

Dans une première étape, on mélange en continu et en chauffant le ou les polymères à l'état fondu aux différentes charges inorganiques et au peroxyde détaillés dans le tableau 1a.In a first step, the melt polymer (s) is continuously blended with the various inorganic fillers and peroxide detailed in Table 1a.

Le mélange est effectué à l'aide d'un mélangeur monovis Buss ou d'une extrudeuse bivis et les charges inorganiques et le peroxyde sont ajoutés au(x) polymère(s) à l'aide d'une trémie doseuse classique.The mixing is carried out using a Buss single-screw mixer or a twin-screw extruder and the inorganic fillers and peroxide are added to the polymer (s) using a conventional metering hopper.

Le mélange du ou des polymères chargés est extrudé directement sur un fil de cuivre massif ou multibrin d'une section de 1,5 mm2, la couche isolante extrudée ayant une épaisseur de 0,8 mm.The mixture of the charged polymer (s) is extruded directly onto a solid or multi-stranded copper wire with a cross-section of 1.5 mm 2 , the extruded insulating layer having a thickness of 0.8 mm.

Les conditions de température de mélange et d'extrusion sont telles que la température est suffisante pour ramollir et homogénéiser le peroxyde et les charges inorganiques dans le ou les polymères tout en évitant d'amorcer la décomposition du peroxyde.The mixing and extrusion temperature conditions are such that the temperature is sufficient to soften and homogenize the peroxide and the inorganic fillers in the polymer (s) while avoiding initiating the decomposition of the peroxide.

Dans une deuxième étape, la couche isolante ainsi formée est réticulée par voie peroxyde sous l'action de la chaleur, en bain de sel, en tube vapeur ou en lit fluidisé à la pression atmosphérique ou à une pression voisine de cette dernière.In a second step, the insulating layer thus formed is crosslinked by the peroxide route under the action of heat, in a salt bath, in a vapor tube or in a fluidized bed at atmospheric pressure or at a pressure close to the latter.

Essais de résistances au feu Fire resistance tests

Les essais de résistances au feu sont effectués selon les trois normes suivantes : IEC 60331 part 21 ou 23, DIN 4102 part 12, et EN 50200.The fire resistance tests are carried out according to the following three standards: IEC 60331 part 21 or 23, DIN 4102 part 12, and EN 50200.

La norme IEC 60331 part 21 ou 23 consiste à soumettre un câble électrique à sa tension nominale lorsqu'il est suspendu horizontalement au-dessus d'une flamme d'au moins 750°C pendant une durée déterminée mais sans contrainte mécanique.The standard IEC 60331 part 21 or 23 consists of subjecting an electric cable to its nominal voltage when it is suspended horizontally over a flame of at least 750 ° C for a determined period but without mechanical stress.

On vérifie sur cette période s'il y a court-circuit ou rupture des conducteurs électriques. L'essai est réussit lorsqu'il n'y a ni court-circuit, ni rupture des conducteurs électriques pendant l'essai et les 15 minutes qui suivent. Le câble électrique ayant satisfait au test pendant 30 minutes est alors classé FE30. Lorsqu'il satisfait au test pendant 90 minutes ou pendant 180 minutes, il est respectivement classé FE90 et FE180.This period is checked whether there is a short-circuit or breakage of the electrical conductors. The test is successful when there is no short circuit or breakage of the electrical conductors during the test and the next 15 minutes. The electrical cable that has passed the test for 30 minutes is then classified FE30. When it passes the test for 90 minutes or 180 minutes, it is respectively classified FE90 and FE180.

La norme DIN 4102 part 12 consiste à soumettre un câble électrique avec ses dispositifs de fixation dans un four de 3 mètres de long minimum pendant une durée déterminée selon une courbe de température normalisée (ISO 834).DIN 4102 part 12 consists in subjecting an electric cable with its fixing devices in an oven of at least 3 meters in length for a determined period of time according to a standard temperature curve (ISO 834).

De plus, le câble électrique et ses dispositifs de fixation sont soumis au poids maximal admissible et aux charges prescrites. Les conducteurs électriques étant sous leur tension de service ne doivent ni se rompre, ni donner lieu à des court-circuits.In addition, the electrical cable and its fasteners are subject to the maximum permissible weight and specified loads. Electrical conductors under their operating voltage must not break or give rise to short circuits.

Ce type d'essai proche de la réalité d'un incendie porte non seulement sur le câble électrique mais aussi sur les systèmes de fixation dudit câble.This type of test close to the reality of a fire relates not only to the electric cable but also to the fastening systems of said cable.

Le câble électrique ayant satisfait à l'essai pendant 30 minutes à 842°C est alors classé E30. Lorsqu'il satisfait à l'essai pendant 60 minutes à 945°C ou pendant 90 minutes à 1006°C, il est alors respectivement classé E60 et E90.The electrical cable having passed the test for 30 minutes at 842 ° C is then classified E30. When it passes the test for 60 minutes at 945 ° C or for 90 minutes at 1006 ° C, it is then respectively classified E60 and E90.

La norme EN 50200 consiste à monter et à fixer par des bagues métalliques un câble électrique présentant la forme d'un U sur une plaque de matériau réfractaire.The EN 50200 standard consists of mounting and fixing by means of metal rings an electric cable in the form of a U on a plate of refractory material.

Le câble électrique pendant l'essai est soumis à une flamme (850°C) ainsi qu'à un choc métallique asséné via une barre métallique qui tombe sur la plaque de matériau réfractaire toutes les 5 minutes. Les conducteurs électriques étant sous leur tension de service ne doivent ni se rompre, ni donner lieu à des courts-circuits.The electrical cable during the test is subjected to a flame (850 ° C) as well as a metal shock delivered via a metal bar which falls on the plate of refractory material every 5 minutes. Electrical conductors being under their operating voltage must not break or give rise to short circuits.

Le câble électrique ayant satisfait à l'essai pendant 15, 30, 60, 90 ou 120 minutes est alors respectivement classé PH15, PH30, PH60 PH90 ou PH120.The electrical cable having satisfied the test for 15, 30, 60, 90 or 120 minutes is then respectively classified PH15, PH30, PH60 PH90 or PH120.

Le tableau 2 ci-après montre les résultats très satisfaisants des essais de résistance au feu de couches isolantes de câbles électriques selon la présente invention. Les câbles électriques utilisés pour lesdits essais sont constitués au moins de deux fils de cuivre respectivement isolés, l'ensemble des ces fils de cuivre isolés étant entouré par une gaine classique de protection de type HFFR bien connu de l'homme du métier. Les couches électriquement isolantes des fils de cuivre de chaque ensemble sont respectivement obtenues à partir des compositions A1 à A3, B1 à B4 et C1 à C3. Tableau 2 Normes IEC 60331 part 31 EN 50200 DIN 4102 Résultats FE 180 PH 90 E30 Table 2 below shows the very satisfactory results of the fire resistance tests of insulating layers of electric cables according to the present invention. The electrical cables used for said tests consist of at least two copper wires respectively insulated, all of these insulated copper son being surrounded by a conventional type of protection HFFR well known to those skilled in the art. The electrically insulating layers of the copper wires of each set are respectively obtained from compositions A1 to A3, B1 to B4 and C1 to C3. <b><u> Table 2 </ u></b> standards IEC 60331 part 31 EN 50200 DIN 4102 Results FE 180 PH 90 E30

Essais de cohésionCohesion tests

Afin de caractériser la cohésion (cohésion résiduelle) d'un matériau après combustion, les couches isolantes extrudées obtenues respectivement à partir des compositions A2, A4, A5 et A6 ont subi un test de résistance mécanique à la pénétration.In order to characterize the cohesion (residual cohesion) of a material after combustion, the extruded insulation layers obtained respectively from the compositions A2, A4, A5 and A6 were subjected to a mechanical penetration resistance test.

Le mode opératoire consiste principalement à enfoncer un organe pénétrant à vitesse constante dans chaque résidu de combustion, et concomitamment à mesurer au moyen d'un capteur de force, la résistance de la matière brûlée en fonction de la profondeur de pénétration effective.The procedure consists mainly in driving a penetrating member at constant speed into each combustion residue, and simultaneously measuring, by means of a force sensor, the resistance of the burnt material as a function of the effective depth of penetration.

L'organe pénétrant se présente concrètement sous la forme d'un cylindre de 6mm de diamètre et de 20mm de longueur. Afin d'offrir une surface de contact convexe, ce cylindre est utilisé suivant une position parallèle à la surface extérieure du résidu à tester, et avec une direction de déplacement perpendiculaire à ladite surface extérieure. La vitesse de pénétration est fixée à 10mm/min.The penetrating member is concretely in the form of a cylinder 6mm in diameter and 20mm in length. In order to provide a convex contact surface, this cylinder is used in a position parallel to the outer surface of the residue to be tested, and with a direction of displacement perpendicular to said outer surface. The penetration speed is set at 10mm / min.

La géométrie cylindrique de l'organe pénétrant permet de quantifier simultanément la résistance à la compression et la résistance au fluage.The cylindrical geometry of the penetrating member makes it possible simultaneously to quantify the compressive strength and the creep resistance.

Dans la pratique, une machine de compression de type Zwick/Roel Z010® est utilisée pour effectuer en continu des séries de mesures de résistance à partir desquelles sera déduite à chaque fois la valeur caractéristique de la cohésion résiduelle, à savoir la force de résistance maximale atteinte après avoir pénétré 50% de l'épaisseur de l'échantillon.In practice, a Zwick / Roel Z010 ® type compression machine is used to continuously perform series of resistance measurements from which the characteristic value of the residual cohesion, ie the maximum resistance force, will be deduced each time. reached after penetrating 50% of the thickness of the sample.

Le tableau 3 ci-après rassemble les valeurs caractéristiques de cohésion résiduelle, notées Fmax-50% exprimée en Newton, pour les couches isolantes extrudées après une combustion à 920°C. Tableau 3 Couches isolantes extrudées obtenues à partir des compositions suivantes : A2 A4 A5 A6 Fmax-50% après combustion à 920°C 231 338 125 215 Table 3 below collates the characteristic values of residual cohesion, denoted Fmax-50% expressed in Newton, for the insulating layers extruded after a combustion at 920 ° C. <b><u> Table 3 </ u></b> Extruded insulating layers obtained from the following compositions: A2 A4 AT 5 A6 Fmax-50% after combustion at 920 ° C 231 338 125 215

Au vu des résultats du tableau 3, la couche isolante obtenue à partir des compositions selon l'invention (compositions A2, A4 et A6) présente une excellente cohésion résiduelle après avoir subi une combustion à 920°C.In view of the results in Table 3, the insulating layer obtained from the compositions according to the invention (compositions A2, A4 and A6) has excellent residual cohesion after being burned at 920 ° C.

Au contraire, le résultat de cohésion résiduelle (125N après une combustion à 920°C) correspondant à la couche isolante obtenue à partir de la composition A5 (composée entre autres de kaolinite c'est-à-dire d'un phyllosilicate ne comprenant pas d'oxyde de potassium) est bien inférieur à ceux obtenus à partir des couches isolantes de l'invention.On the contrary, the residual cohesion result (125N after combustion at 920 ° C.) corresponding to the insulating layer obtained from the composition A5 (composed inter alia of kaolinite, that is to say of a phyllosilicate not comprising potassium oxide) is much lower than those obtained from the insulating layers of the invention.

Par conséquent, ces résultats permettent avantageusement de montrer l'existence d'une réelle synergie d'action de l'association des composés b, c et d sur le paramètre mesuré (i.e. cohésion résiduelle).Consequently, these results advantageously make it possible to show the existence of a real synergy of action of the combination of compounds b, c and d on the measured parameter (i.e. residual cohesion).

Claims (15)

  1. A power and/or telecommunications cable comprising at least one conducting element surrounded by at least one insulating layer extending along the cable, the insulating layer being obtained from a composition including the following compounds: a) an organic polymer, b) an inorganic compound including a potassium oxide and/or one of its precursors, c) a boron oxide and/or one of its precursors, and d) calcium oxide CaO and/or one of its precursors, characterized in that the quantity of the compound d is at least 10% by weight of the total weight of compounds b, c and d in the composition.
  2. The cable according to claim 1, characterized in that the quantity of the compound b is at least 2 parts by weight per 100 parts by weight of polymer(s) in the composition.
  3. The cable according to claim 1 or 2, characterized in that the quantity of compound b is at least 2% by weight of the total weight of compounds b, c and d in the composition.
  4. The cable according to any one of the preceding claims, characterized in that the quantity of compound c is at least 20 parts by weight per 100 parts by weight of polymer(s) in the composition.
  5. The cable according to any one of the preceding claims, characterized in that the quantity of compound c is at least 10% by weight of the total weight of compounds b, c and d in the composition.
  6. The cable according to any one of the preceding claims, characterized in that the quantity of the compound d is at least 10 parts by weight per 100 parts by weight of polymer(s) in the composition.
  7. The cable according to any one of the preceding claims, characterized in that compound b is a layer silicate including a potassium oxide.
  8. The cable according to claim 7, characterized in that compound b is a mica, preferably muscovite mica.
  9. The cable according to claim 7 or 8, characterized in that the quantity of compound b is at least 40% by weight of the total weight of compounds b, c and d in the composition.
  10. The cable according to any one of claims 7 to 9, characterized in that the composition includes a quantity of compound b of 40 to 80% by weight, a quantity of compound c of 10 to 30% by weight, and a quantity of compound d of 10 to 50% by weight, said quantities being defined in relation to the total weight of compounds b, c and d in the compound.
  11. The cable according to any one of claims 7 to 10, characterized in that the composition includes a quantity of compound b of 60% by weight, a quantity of compound c of 20% by weight, and a quantity of compound d of 20% by weight, said quantities being defined in relation to the total weight of compounds b, c and d in the composition.
  12. The cable according to any one of the preceding claims, characterized in that the boron oxide precursor is chosen from among zinc borate, boron phosphate, boric acid, calcium borate, and sodium borate.
  13. The cable according to any one of the preceding claims, characterized in that the boron oxide precursor is dehydrated.
  14. The cable according to any one of the preceding claims, characterized in that the calcium oxide precursor is calcium carbonate.
  15. The cable according to any one of the preceding claims, characterized in that the composition is cross-linked.
EP09737074A 2008-07-28 2009-07-16 Ceramisable composition for a power and/or telecommunication cable Not-in-force EP2319053B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0855147A FR2934410A1 (en) 2008-07-28 2008-07-28 CERAMIZABLE COMPOSITION FOR POWER CABLE AND / OR TELECOMMUNICATION
PCT/FR2009/051423 WO2010012932A1 (en) 2008-07-28 2009-07-16 Ceramisable composition for a power and/or telecommunication cable

Publications (2)

Publication Number Publication Date
EP2319053A1 EP2319053A1 (en) 2011-05-11
EP2319053B1 true EP2319053B1 (en) 2012-10-31

Family

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Application Number Title Priority Date Filing Date
EP09737074A Not-in-force EP2319053B1 (en) 2008-07-28 2009-07-16 Ceramisable composition for a power and/or telecommunication cable

Country Status (8)

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US (1) US20110186330A1 (en)
EP (1) EP2319053B1 (en)
KR (1) KR20110053439A (en)
CN (1) CN102113063A (en)
AU (1) AU2009275738A1 (en)
CL (1) CL2011000106A1 (en)
FR (1) FR2934410A1 (en)
WO (1) WO2010012932A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2819026T3 (en) 2010-09-10 2021-04-14 Prysmian Spa Fire resistant optical cable
RU2567955C2 (en) * 2013-07-24 2015-11-10 Федеральное государственное бюджетное учреждение науки Институт синтетических полимерных материалов им. Н.С. Ениколопова Российской академии наук (ИСПМ РАН) Composition, based on liquid low-molecular siloxane caoutchouc for fireproof material
KR101696339B1 (en) * 2016-04-26 2017-01-17 주식회사 호니시스 Improvement device of energy efficiency using electron density increase
KR102067665B1 (en) * 2018-05-10 2020-01-17 넥쌍 Cable comprising crosslinked layer obtained from polymer composition

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Publication number Priority date Publication date Assignee Title
US4225649A (en) * 1978-09-27 1980-09-30 The Flamemaster Corporation Fire retardant composition and cables coated therewith
JPS6213486A (en) * 1985-07-10 1987-01-22 Hitachi Cable Ltd Fireproof composition in putty form
US6043312A (en) * 1989-06-27 2000-03-28 The Furon Company Low flame and smoke compositions for plenum cables
ES2145330T3 (en) * 1995-01-23 2000-07-01 Bayer Ag GELIFIERS, FIRE FIGHTING GELS AND FIRE FIGURE GLASSES.
WO2000059841A1 (en) * 1999-04-01 2000-10-12 Imerys Pigments, Inc. Kaolin clay pigments, their preparation and use
JP2006503121A (en) * 2002-08-01 2006-01-26 セラム ポリメリック ピーティーワイ リミテッド Fire resistant silicone polymer composition
JP2004095373A (en) * 2002-08-30 2004-03-25 Tokai Rubber Ind Ltd Insulating tape for flexible flat cable and flexible flat cable using it
TWI322176B (en) * 2002-10-17 2010-03-21 Polymers Australia Pty Ltd Fire resistant compositions
US7138448B2 (en) * 2002-11-04 2006-11-21 Ciba Specialty Chemicals Corporation Flame retardant compositions
FR2859814A1 (en) * 2003-09-12 2005-03-18 Nexans Electrically-insulating and heat-resistant composition, especially for use in security cables for power or telecommunications, contains organic polymer, phyllosilicate and refractory filler
WO2005121234A2 (en) * 2005-08-22 2005-12-22 Solvay Advanced Polymers, L.L.C. Flame retarded polymer composition with improved thermal stability

Also Published As

Publication number Publication date
CN102113063A (en) 2011-06-29
KR20110053439A (en) 2011-05-23
WO2010012932A1 (en) 2010-02-04
FR2934410A1 (en) 2010-01-29
EP2319053A1 (en) 2011-05-11
US20110186330A1 (en) 2011-08-04
CL2011000106A1 (en) 2011-04-29
AU2009275738A1 (en) 2010-02-04

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