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    • 专利摘要:
    The present invention relates to a device comprising a cable and / or a cable accessory, said cable and / or said cable accessory comprising at least one composite layer obtained from a composite composition based on at least one derivative cellulose, at least one organic compound having a boiling or decomposition temperature higher than approximately 100 ° C. and at least one cement composition chosen from an aluminosilicate geopolymer composition and a magnesium-based composition, as well as 'to a method of manufacturing such a device.
    公开号:FR3075453A1
    申请号:FR1762516
    申请日:2017-12-19
    公开日:2019-06-21
    发明作者:Thierry Auvray；Franck GYPPAZ；Nicolas Estreboou
    申请人:Nexans SA；
    IPC主号:
    专利说明:

    (57) The present invention relates to a device comprising a cable and / or a cable accessory, said cable and / or said cable accessory comprising at least one composite layer obtained from a composite composition based on at at least one cellulose derivative, at least one organic compound having a boiling or decomposition temperature greater than approximately 100 ° C. and at least one cement composition chosen from an aluminosilicate geopolymer composition and a magnesium-based composition , as well as a method of manufacturing such a device.
    DEVICE COMPRISING A CABLE OR A CABLE ACCESSORY CONTAINING A FIRE RESISTANT COMPOSITE LAYER
    The present invention relates to a device comprising a cable and / or a cable accessory, said cable and / or said cable accessory comprising at least one composite layer obtained from a composite composition based on at least one derivative cellulose, at least one organic compound having a boiling or decomposition temperature greater than approximately 100 ° C., and at least one cement composition chosen from an aluminosilicate geopolymer composition and a magnesium-based composition, as well than to a process for manufacturing such a device.
    It typically but not exclusively applies to electrical and / or optical cables intended for the transport of energy and / or for the transmission of data, in particular to fire-resistant electrical and / or optical safety cables, particularly halogen-free, susceptible operate for a given period of time under fire conditions, without being either a fire propagator or a generator of significant smoke; as well as their accessories such as junctions and / or terminations. These safety cables are in particular medium voltage energy transport cables (in particular from 6 to 45-60 kV) or low frequency transmission cables, such as control or signaling cables.
    An energy and / or telecommunication cable is a cable intended for the transport of electrical energy and / or for data transmission. It conventionally comprises one or more insulated conductive elements, or in other words one or more conductor (s) (electrical (s) and / or optical (s)) elongated surrounded by at least one layer electrically insulating. The electrically insulating layer can typically be an electrically insulating polymer layer possibly in physical contact with the electrical and / or optical conductor (s). Said or said insulated conductive elements are surrounded by an external protective sheath intended to mechanically protect the insulated conductive element (s).
    In some cable constructions, there is only one layer which performs the two functions of electrical insulation and protective sheath.
    The materials generally used to form the electrically insulating layer and / or said protective sheath are composite materials based on polymers, for example silicone polymers, and various additives, in particular reinforcing fillers such as silica, and flame retardant fillers (or flame retardants) intended to improve their fire resistance.
    Despite the presence of such charges, the fire resistance of these insulating layers is not always entirely satisfactory.
    In order to make one or more cables resistant to fire, it is known to cover said cables with an electrically insulating layer comprising several superimposed insulating strips comprising mica and glass fibers, and a polymeric binder (eg polyorganosiloxane) in contact with each. said insulating strips. However, the production cost of said electrically insulating layer is high (i.e. very long preparation time) and it has a large footprint.
    Other materials such as stone, brick, cement, lead, steel, concrete, rock wool, ceramics, geopolymers, etc. have fire resistance properties.
    In particular, geopolymers are essentially mineral chemical compounds or mixtures of compounds made up of units of the silico-oxide (-Si-O-Si-O-), silico-aluminate (-Si-O-AI-O-) type. , ferro-silico-aluminate (-Fe-O-Si-O-AI-O-), or alumino-phosphate (-AI-OPO-), created by a geopolymerization process (ie polycondensation). Geopolymers are generally able to polymerize and harden at room temperature (geopolymer cements). It is also possible to accelerate the rate of polymerization and therefore the hardening of the geopolymers by subjecting them to a heat treatment. The exact mechanism of geopolymerization is still unknown due in particular to the speed of the reaction. The most common geopolymers are those based on aluminosilicates designated under the term "poly (sialate)" [or "poly (silico-oxo-aluminate" or (-Si-O-AI-O-) n with n denoting the degree These aluminosilicate geopolymers result from the polycondensation of oligomers of oligo (sialate) type generally formed from a mixture of at least one source of aluminum, at least one source of silicon, an alkaline reagent and d Geopolymers based on aluminosilicates have been grouped into three families according to the atomic ratio Si / AI, which can be equal to 1, 2 or 3. A distinction is made between poly (sialates) corresponding to the formula M n (- Si-O-AI-O-) n or (M) -PS, the poly (sialate-siloxos) corresponding to the formula M n (-Si-O-AI-O-Si-O-) n or (M) -PPS, and the poly (sialate-disiloxos) corresponding to the formula M n (-Si-O-AI-O-Si-O-Si-O) n or (M) -PSDS, with M representing at least one cation alkaline or alkaline earth such as K, Na, Li, Cs or Ca and n denoting the degree of polymerization.
    Geopolymers are used in many applications: design of new materials in the fields of civil engineering and construction, creation of sculptures, manufacture of partitions and fire doors for fire protection, manufacture of coatings of a substrate, mortar, adhesive or molding material, manufacture of flexible fire panels used for fire protection of openings in walls, and also cable passages, and most recently as a structure of the "black box" embedded in planes.
    In particular, international application WO 2016/051049 A1 describes a fire-resistant layer, used as a junction layer of two fire-resistant cables, comprising at least one cementitious material such as a geopolymer cement. The layer may further comprise polymeric additives such as cellulose acetate or other unspecified cellulose derivatives. However, this solution is not suitable, in particular in terms of flexibility and adhesion, in order to be able to serve as a fire-resistant layer in an electric cable and / or data transmission and / or in a cable accessory, in particular during of a fire.
    The object of the present invention is to overcome the drawbacks of the techniques of the prior art by proposing a cable and / or a cable accessory, comprising at least one layer having good mechanical properties, in particular in terms of flexibility and adhesion. , while guaranteeing good fire resistance and an advantageous cost price.
    Another object of the invention is to provide a simple, economical process, easy to implement, making it possible to manufacture a cable and / or a cable accessory, comprising at least one layer which has good mechanical properties, in particular in terms of flexibility and adhesion, prevents the propagation of the flame, resists fire in order to function as long as possible, and limits its degradation in extreme thermal conditions such as a fire.
    The present invention first relates to a device comprising an energy and / or telecommunication cable, and / or an accessory for an energy and / or telecommunication cable, characterized in that said cable and / or said accessory for cable comprises at least one composite layer obtained from a composite composition comprising at least one organic compound having a boiling or decomposition temperature greater than approximately 100 ° C., at least one cellulose derivative, and at least one cementitious composition chosen from an aluminosilicate geopolymer composition and a magnesium-based composition comprising a magnesium silicate, an alkali silicate, an alkaline base and water.
    The cement composition is an inorganic composition.
    It preferably includes:
    - some water,
    - silicon (Si),
    - aluminum (Al) or magnesium (Mg),
    - oxygen (O), and
    - at least one element chosen from potassium (K), sodium (Na), lithium (Li), cesium (Cs) and calcium (Ca).
    The magnesium-based composition preferably comprises water, silicon (Si), magnesium (Mg), oxygen (O), and at least one element chosen from potassium (K), sodium ( Na), lithium (Li), cesium (Cs), and calcium (Ca), and preferably chosen from potassium (K) and sodium (Na).
    The aluminosilicate geopolymer composition preferably comprises water, silicon (Si), aluminum (Al), oxygen (O), and at least one element chosen from potassium (K), sodium ( Na), lithium (Li), cesium (Cs), and calcium (Ca), and preferably chosen from potassium (K) and sodium (Na).
    According to a particularly preferred embodiment of the invention, the aluminosilicate geopolymer composition comprises an alkaline silicate, an aluminosilicate, water, and optionally an alkaline base.
    In the present invention, the cement composition is capable of forming a cement material.
    In particular, the aluminosilicate geopolymer composition is capable of forming an aluminosilicate geopolymer. The ingredients of the aluminosilicate geopolymer composition can therefore undergo polycondensation to form an aluminosilicate geopolymer. Indeed, geopolymers result from a mineral polycondensation reaction by alkaline activation, called geosynthesis, as opposed to traditional hydraulic binders in which hardening is the result of hydration of calcium aluminates and calcium silicates.
    The magnesium-based composition is capable of forming a cementitious material with a texture similar to that obtained with the aluminosilicate geopolymer composition.
    Consequently, the cement composition of the invention is different from a ceramic composition or powder.
    The cement composition is in the liquid form which makes it possible to form, with the cellulose derivative and the organic compound having a boiling or decomposition temperature greater than approximately 100 ° C., a homogeneous composite composition, in particular in the form of a homogeneous composite paste.
    The alkali silicate of the cement composition can be chosen from sodium silicates, potassium silicates, and one of their mixtures. The alkaline silicates sold by the company Silmaco and by the company PQ Corporation are preferred. The alkali silicate is preferably a sodium silicate.
    When it is present, the alkaline base of the cement composition can be chosen from KOH, NaOH, and mixtures thereof.
    The aluminosilicate of the aluminosilicate geopolymer composition can be chosen from kaolins such as metakaolins (ie calcined kaolins), fly ash (well known under Anglicism "fl y ash"), blast furnace slag (well known under blast furnace slag), swelling clays such as bentonite, calcined clays, any type of compound comprising aluminum and fumed silica, zeolites, and one of their mixtures.
    Among these compounds, metakaolins are preferred, in particular those sold by the company Imérys.
    The magnesium silicate of the magnesium composition can be talc.
    According to a particularly preferred embodiment of the invention, the magnesium-based composition comprises from 10 to 50% by mass approximately of a magnesium silicate, from 8 to 35% by mass approximately of an alkali silicate, from 5 at about 20% by mass of an alkaline base, and from 10 to 55% by mass approximately of water.
    According to a particularly preferred embodiment of the invention, the aluminosilicate geopolymer composition comprises from 10 to 50% by mass approximately of an aluminosilicate, from 8 to 35% by mass approximately of an alkali silicate, from 0 to 10% by weight approximately by mass of an alkaline base, and from 10 to 55% by mass approximately of water.
    In particular, the aluminosilicate geopolymer composition comprises from 25 to 65% by mass approximately of solid materials (aluminosilicate, alkali silicate and alkaline base when it is present), and preferably from 40 to 60% by mass approximately, relative to the total mass of said composition.
    The cement composition is in the form of a liquid at room temperature (e.g. 18-25 ° C).
    The cement composition preferably represents from 30 to 80% by mass approximately, and even more preferably from 35 to 70% by mass approximately, relative to the total mass of the composite composition.
    The cement composition is preferably an aluminosilicate geopolymer composition.
    The composite composition further comprises a cellulose derivative.
    In the present invention, the expression “cellulose derivative” means a functionalized cellulose, in particular functionalized at the level of its hydroxyl functions.
    The cellulose derivative is preferably a cellulose ester or a cellulose ether.
    Examples of cellulose esters that may be mentioned include cellulose acetate, cellulose triacetate, cellulose propionate, cellulose acetopropionate or cellulose acetate butyrate.
    Mention may be made, as examples of cellulose ethers, of methylhydroxyethylcellulose (MHEC), hydroxymethylethylcellulose (HMEC), carboxymethylcellulose (CMC), methylcellulose (MC), ethylcellulose (EC), hydroxyethylcellulose ( HEC), hydroxyethylpropylcellulose (HEPC), hydroxypropylmethylcellulose (HPMC) or a salt of one of the abovementioned compounds (such as a salt of an alkali metal such as for example a sodium salt).
    Carboxymethylcellulose (CMC) is preferred.
    According to the invention, the cellulose derivative preferably represents from 3 to 20% by mass approximately, and even more preferably from 5 to 15% by mass approximately, relative to the total mass of the composite composition.
    The organic compound having a boiling or decomposition temperature above 100 ° C. makes it possible in particular to promote the dissolution of the cellulose derivative in the composite composition.
    The organic compound preferably has a boiling or decomposition temperature greater than or equal to 140 ° C, and more preferably still greater than or equal to 160 ° C.
    Said organic compound is preferably miscible in water. This thus makes it possible to form a homogeneous composite composition in the presence of the cement composition.
    Said organic compound is preferably chosen from polyols, in particular those comprising from 2 to 12 carbon atoms.
    Among the polyols, mention may be made of xylitol, sorbitol, mannitol, maltitol, lactitol, isomalt, glycerol, dulcitol, iditol, ethylene glycol or propylene glycol.
    According to the invention, the organic compound preferably represents from 15 to 50% by mass approximately, and even more preferably from 20 to 40% by mass approximately, relative to the total mass of the composite composition.
    The organic compound can be solid or liquid at room temperature (e.g. 18-25 ° C), and preferably liquid at room temperature.
    The composite composition may also comprise one or more additives, in particular chosen from starch, a plasticizer, an inert filler, a dye, an organic additive with a polymer structure, a crosslinking agent and one of their mixtures.
    Such an additive, when present, preferably represents from 0.1 to 10% by mass approximately, and more preferably from 2 to 5% by mass approximately, relative to the total mass of the composite composition.
    The starch generally comprises amylose, amylopectin, and optionally phytoglycogen.
    By way of example (and depending on the source), the starch comprises from 15 to 30% by mass of amylose, from 70 to 85% by mass approximately of amylopectin, and from 0 to 20% by mass of phytoglycogen, based on the total mass of the starch.
    The starch can be a native starch or a modified starch, and preferably a native starch.
    Native starch can be a starch from cereals (eg wheat, corn, barley, triticale, sorghum or rice), tubers (eg potato or cassava), legumes (eg peas or soy), roots, bulbs , stems, fruit or a mixture thereof.
    The modified starch can be a physically, chemically or enzymatically modified starch.
    The modified starch can be chosen from oxidized starches, starches hydrolysed by the acid, oxidizing or enzymatic route, modified (e.g. functionalized) starches by physico-chemical route, such as in particular esterified and / or etherified starches.
    Functionalization can be obtained by acetylation in aqueous phase with acetic anhydride, reactive extrusion of acid anhydrides, mixed anhydrides, fatty acid chlorides, caprolactone oligomers or lactides, by hydroxypropylation in the glue phase, by cationization in the dry phase or in the glue phase, by crosslinking, by anionization by phosphating or by succinylation, by silylation, by butadiene telomerization, etc.
    Oxidized starches are preferred.
    The plasticizer can be intended to improve the dispersion of starch within the composite layer (starch plasticizer) or be used as an implementing agent (well known under Anglicism "processing aid") .
    The plasticizer can be a metal stearate, an ethylene glycol, a polyol like glycerol, sorbitol, mannitol, maltitol, xylitol, a sucrose like glucose or fructose, a plasticizer containing amide groups, any type of plasticizer based on modified polysaccharide (s) or a mixture thereof.
    The preferred plasticizer is a metal stearate such as zinc stearate.
    The inert filler can be chosen from talc, phyllosilicates, hydrated hydroxides such as aluminum hydroxide (ATH) or magnesium hydroxide (MDH), silicas, borates, micas, and kaolins.
    Talc is preferred.
    The dye is preferably a dye that is liquid at room temperature (i.e. at 18-25 ° C).
    The organic additive with a polymer structure is preferably chosen from polyolefin fibers such as polypropylene fibers, high density polyethylenes (HDPE), aramides, and technical glass fibers coated with silicone or an organic polymer of polyethylene type, and one of their mixtures.
    The crosslinking agent can be a crosslinking agent of the cellulose derivative.
    The composite layer is preferably fire resistant.
    Thanks to the combination of a cellulose derivative and a cementitious material obtained from the cementitious composition, a flexible and / or flexible composite layer can be formed and this retains its elasticity over time. This layer therefore has good flexibility and adhesion properties, while ensuring good fire resistance. The cellulose derivative guarantees the elasticity of the composite layer and its adhesion to the layer of the cable with which it is intended to be in direct physical contact; and the cementitious material, meanwhile, ensures the fire resistance of the composite layer.
    In other words, the composite layer of the device of the invention is a homogeneous organic / inorganic hybrid layer. In particular, this homogeneity is obtained thanks to the combination within the composite layer of a cementitious material (in particular an aluminosilicate geopolymer) and a cellulose derivative.
    The composite layer of the invention comprises a cellulose derivative, an organic compound having a boiling or decomposition temperature greater than 100 ° C., and a cementitious material chosen from an aluminosilicate geopolymer and a magnesium-based material, the the aforementioned compounds being as defined in the invention.
    The composite layer of the invention preferably comprises from 10 to 60% by mass approximately of cementitious material, and even more preferably from 20 to 50% by mass approximately of cementitious material, relative to the total mass of the composite layer.
    The composite layer of the invention preferably comprises from 3 to 20% by mass approximately of cellulose derivative, and even more preferably from 5 to 15% by mass approximately of cellulose derivative, relative to the total mass of the composite layer .
    The composite layer can also comprise from 0.01 to 30% of water and / or from 0.01 to 15% of organic compound, in particular originating from the process for preparing said layer as described below. The water and the organic compound, which optionally serve to dissolve or disperse the cellulose derivative and the constituents of the cement composition to prepare the composite composition, may not be completely eliminated at the end of the process. The water and / or the organic compound are then found for example in the form of molecules forming non-covalent bonds (e.g. Van der Waals bonds) with the other compounds of the layer.
    The cementitious material is preferably an aluminosilicate geopolymer.
    Advantageously, the device according to the invention meets at least any one of the following fire resistance standards: EN50200, IEC60331-1, EN50399, IEC60331-11, IEC60331-21, IEC60331-23, IEC6033125, DIN4102, NBN713020 addendum 3, EN50577, NFC32070 CRI,
    IEC600332-1 and BS6387CWZ.
    Advantageously, the composite layer defined above satisfies the fire resistance standard IEC 60331-11, with electric cables under a voltage of 10 kV exposed to a temperature of approximately 750 ° C for 120 minutes.
    The composite layer of the invention can be an extruded layer, a ribbon layer (i.e. in the form of a ribbon or a strip), or a layer in the form of a padding.
    When the composite layer is an extruded or banded layer, it preferably has a substantially constant thickness and in particular constitutes a continuous protective envelope.
    The composite layer preferably has a thickness ranging from 2 to 6 mm approximately, and more preferably ranging from 3 to 5 mm approximately.
    When the thickness of the composite layer is less than 1.5 mm, the thermal protection of the device of the invention is not sufficient.
    The composite layer preferably comprises an aluminosilicate geopolymer having an Si / Al molar ratio ranging from 1 to 35, and preferably ranging from 1.9 to 3.
    The aluminosilicate geopolymer of the composite layer can be chosen from poly (sialates) corresponding to the formula (I) M n (-Si-O-AI-O-) n [(M) -PS], poly (sialate- siloxos) corresponding to the formula (II) M n (-Si-O-AI-OSi-O-) n [(M) -PPS], and the poly (sialate-disiloxos) corresponding to the formula (III) M n (-Si-O-AI-O-Si-O-Si-O) n [(M) -PSDS], formulas in which M represents at least one alkaline cation K, Na, Li, Cs or one of their mixtures, and n denoting the degree of polymerization. In the compound of formula (I), the Si / AI molar ratio is 1, in the compound of formula (II), the Si / AI molar ratio is 2, and in the compound of formula (III), the ratio Si / AI molar is 3.
    The composite layer of the invention is preferably non-porous.
    The composite layer of the invention is preferably an electrically insulating layer.
    In the present invention, the term "electrically insulating layer" means a layer whose electrical conductivity can be at most 1.10 ' 9 S / m, and preferably at most 1.10' 10 S / m (siemens per meter) (at around 25 ° C).
    Thanks to the presence of the composite layer, the device according to the invention has good mechanical properties while having excellent fire resistance. In particular, the composite layer is flexible enough to allow the handling of the cable (e.g. winding, bending, twisting) without however causing unacceptable damage to said layer which would have the consequence of reducing its cohesion and its fire resistance. Furthermore, the composite layer remains intact from ambient temperature to the operating temperature of the cable under load (ie under tension) and has the advantage of forming an ordered porous structure from 450 ° C., thus making it possible to provide reinforced protection. against the diffusion of heat for at temperatures greater than or equal to 1000 ° C for a period of up to 120 min, in particular reached during a fire. This porous and rigid structure contains air which by nature is an excellent thermal insulator.
    In other words, the composite layer is transformed under the effect of a high temperature, in particular a temperature ranging from 450 ° C. to 1000 ° C., generally reached during a fire, to form a cohesive residual layer. and porous which protects the cable or the cable accessory, and in particular the underlying layers and / or the elongated conductive element.
    Finally, the composite layer of the invention has good elasticity or flexibility, making it possible to use it in the form of a ribbon or strip.
    According to a first variant of the invention, the device comprises an energy and / or telecommunications cable.
    An energy and / or telecommunications cable generally comprises at least one elongated conductive element and at least one external protective sheath, in particular electrically insulating.
    According to a second variant of the invention, the device comprises an accessory for power and / or telecommunications cable.
    A cable accessory may be a junction or a termination which may comprise an assembly of several layers of materials (eg of polymeric materials) generally of the silicone rubber type, possibly one or more reinforcing layers, for example one or more metallic layers, as well as '' an external protective sheath (eg fire-resistant) such as for example an elastomeric tape or a mica strip or an assembly of one or more layers of ethylene-propylene-diene monomer (EPDM), possibly one or more layers metallic, and at least one expanded layer of EPDM, in particular in the form of a shape memory tube.
    The composite layer is preferably an internal layer of said cable or of said cable accessory.
    According to the invention, the term “internal layer” means a layer which does not constitute the outermost layer of the cable or of the cable accessory, and more particularly:
    in the case of a cable, a layer interposed between the elongated conductive element and an external protective sheath, in particular electrically insulating, said layer being or not in direct contact with the elongate conductive element and
    - in the case of a junction or termination, a layer interposed between the external protective sheath and one of the layers of material of silicone rubber type and / or one of the reinforcing layers, said layer being or not in direct contact with said outer sheath.
    The composite layer of the cable of the invention generally covers one or more elongated conductive elements or is positioned on a sheath or internal layer of the cable or of the cable accessory, it then acts as stuffing.
    According to a preferred embodiment, the device is a cable.
    In this case, the cable comprises at least one elongated conductive element and the composite layer as defined in the invention surrounds said elongate conductive element.
    The cable may include a plurality of elongated conductive elements. The composite layer can then surround the plurality of elongated conductive elements of the cable.
    The cable can comprise a plurality of composite layers as defined in the invention.
    According to a first variant of this embodiment, the cable comprises one or more elongated conductive elements and the plurality of composite layers surrounds the elongate conductive element or the plurality of elongate conductive elements.
    For example, the cable can comprise two composite layers as defined in the invention adjacent.
    According to a second variant of this embodiment, the cable comprises a plurality of elongated conductive elements and each of the composite layers individually surrounds each of the elongate conductive elements to form insulated elongate conductive elements.
    The elongated conductive element or elements of the cable of the invention are preferably elongated electrically conductive elements. The cable is therefore an electric cable.
    The cable of the invention may further comprise an external protective sheath, in particular electrically insulating, surrounding the composite layer (s).
    The external protective sheath is preferably made of a halogen-free material. It can be produced conventionally from materials delaying the propagation of the flame or resistant to the propagation of the flame. In particular, if the latter do not contain halogen, we speak of HFFR cladding (for Anglicism “Hatogen Free Flame Retardant”).
    The outer protective sheath represents the outermost layer of the cable. It ensures the mechanical integrity of the cable.
    It comprises at least one organic or inorganic polymer.
    The choice of organic or inorganic polymer is not limiting and these are well known to those skilled in the art.
    According to a preferred embodiment of the invention, the organic or inorganic polymer is chosen from crosslinked and non-crosslinked polymers.
    The organic or inorganic polymer can be a homo- or a co-polymer having thermoplastic and / or elastomeric properties.
    The inorganic polymers can be polyorganosiloxanes.
    The organic polymers can be polyurethanes or polyolefins.
    The polyolefins can be chosen from polymers of ethylene and propylene. Examples of ethylene polymers that may be mentioned include linear low density polyethylene (LLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), copolymers of ethylene and vinyl acetate (EVA), copolymers of ethylene and butyl acrylate (EBA), methyl acrylate (EMA), 2-hexylethyl acrylate (2HEA), ethylene copolymers and alpha-olefins such as for example polyethylene octene (PEO), copolymers of ethylene and propylene (EPR.), terpolymers of ethylene and propylene (EPT) such as for example terpolymers of ethylene propylene diene monomer (EPDM) or a mixture thereof.
    The sheath polymer is preferably an organic polymer, more preferably an ethylene polymer, and more preferably a copolymer of ethylene and vinyl acetate, a linear low density polyethylene or a mixture thereof.
    The external protective sheath may further comprise a hydrated flame retardant mineral filler. This hydrated flame retardant mineral filler acts mainly by physical means by decomposing in an endothermic manner (e.g. release of water), which has the consequence of lowering the temperature of the sheath and limiting the propagation of flames along the cable. We speak in particular of flame retardant properties, well known under Anglicism "flame retardant".
    The hydrated flame retardant mineral filler can be a metal hydroxide such as magnesium hydroxide or aluminum trihydroxide.
    The external protective sheath may further comprise an inert filler, in particular chosen from talc, micas, dehydrated clays and one of their mixtures.
    The second object of the invention is a method of manufacturing a device comprising an energy and / or telecommunication cable and / or an accessory for an energy and / or telecommunication cable as defined according to the first object of the invention. invention, characterized in that it comprises at least the following steps:
    1) the preparation of a composite composition as defined in the invention according to at least the following steps:
    1) the preparation of a cement composition chosen from an aluminosilicate geopolymer composition comprising an aluminosilicate, an alkali silicate, water, and optionally an alkaline base, and a magnesium-based composition comprising a magnesium silicate, an alkali silicate , water, and an alkaline base, ii) the mixture of the cement composition of step i) with a cellulose derivative, an organic compound having a boiling or decomposition temperature greater than approximately 100 ° C. , and possibly water; and
    2) the formation of a composite layer as defined in the invention from the composite composition obtained in step 1):
    - either around one or more elongated conductive elements and / or around a layer of an energy and / or telecommunication cable, when the device is a cable,
    - or around at least one of the layers of a junction or a termination, when the device is a cable accessory.
    The aluminosilicate, the magnesium silicate, the alkaline silicate, the alkaline base, the cellulose derivative and the organic compound having a boiling or decomposition temperature higher than approximately 100 ° C. are as defined in the first object of l 'invention.
    The process according to the invention is quick, simple and advantageous from an economic point of view. It makes it possible to manufacture in a few steps a device having excellent fire resistance, while guaranteeing good mechanical properties, in particular in terms of flexibility.
    An inert filler and / or a dye and / or a starch and / or a starch plasticizer and / or an organic additive with a polymer structure and / or a crosslinking agent as defined in the first subject of the invention can be added during step ii) or after step ii).
    The preparation of the aluminosilicate geopolymer composition according to step i) is generally carried out at a high pH, in particular varying from 10 to 13.
    Step i) preferably comprises the following sub-steps:
    ia) the preparation of an aqueous solution of alkali silicate with a SiO2 / M ' 2 O molar ratio ranging from 1.6 to 35 approximately, and preferably from 1.6 to 4 approximately, M' being an alkali metal, the concentration mass of the alkali silicate in water which can range from 30 to 60% approximately, and preferably from 40 to 60% approximately, and ib) the mixture of an aluminosilicate in the form of powder of molar ratio AI2O3 / S1O2 ranging from 0, 4 to 0.8 approximately with the aqueous alkali silicate solution prepared in the preceding step, the mass concentration of the aluminosilicate in the aqueous alkali silicate solution prepared in the preceding sub-step possibly ranging from approximately 10 to 80%, and preferably from 25% to around 65%.
    The combination of the aqueous alkali silicate solution and the aluminosilicate solution allows the formation of a liquid aluminosilicate geopolymer composition.
    The aqueous alkali silicate solution of sub-step ia) can be prepared by mixing silicon dioxide SiO 2 or an alkali silicate with a base ΜΌΗ in which M 'is preferably K, Na or their mixture.
    Silicon dioxide SiO 2 can be chosen from among silicas such as fumed silica (well known under Anglicism "fumed silica"), quartz, and their mixtures.
    In particular, the alkaline base ΜΌΗ can be dissolved in water resulting in the generation of heat (exothermic reaction), then silicon dioxide SiO 2 or alkali silicate can be added.
    The alkali silicate can be chosen from sodium silicates, potassium silicates, and one of their mixtures. The alkaline silicates sold by the company Silmaco and by the company PQ Corporation are preferred. The alkali silicate is preferably a sodium silicate.
    The aluminosilicate can be chosen from kaolins such as metakaolins (ie calcined kaolins), fly ash (well known under Anglicism "fhy ash"), blast furnace slag (well known under Anglicism "blast furnace slag ”), swelling clays such as bentonite, calcined clays, any type of compound comprising aluminum and fumed silica, zeolites, and one of their mixtures.
    Among these compounds, metakaolins are preferred, in particular those marketed by the company Imérys.
    The magnesium silicate is preferably talc.
    In step ii), water can be particularly useful for dissolving the organic compound when it is a solid or a viscous liquid.
    At the end of step ii), a homogeneous paste is obtained which can then be used in the following step 2).
    Step ii) can be carried out by separately preparing a solution comprising the cellulose derivative, the organic compound and optionally water, then mixing this solution with the cement composition of step i).
    The geopolymer is formed during steps i) and ii).
    When the device is a cable, step 2) can be carried out:
    - by extrusion of said composite composition around one or more elongated conductive elements and / or around a layer of an energy and / or telecommunication cable, or
    - By forming a strip or ribbon from said composite composition, then winding said strip or ribbon around one or more elongated conductive elements and / or around a layer of a cable energy and / or telecommunications.
    When the device is an accessory, step 2) can be carried out by forming a strip or a ribbon from said composite composition, then winding said strip or ribbon around at least one of the layers a junction or termination.
    The extrusion can be carried out at ambient temperature or hot, in particular at a temperature ranging from approximately 60 ° C. to 110 ° C., and preferably from approximately 70 ° C. to 95 ° C.
    The strip or the ribbon can be obtained by extrusion, in particular at a temperature ranging from approximately 20 to 90 ° C. or by calendering at ambient temperature (e.g. 20-25 ° C.).
    The winding can also be carried out with overlap zones.
    According to a particular embodiment of the invention, and when the device is an energy and / or transmission cable, the method can further comprise before, during or after step 2), a step 3) of application of an external protective sheath as defined in the first object of the invention, in particular electrically insulating, around the composite layer.
    The production of this outer protective sheath can in particular be carried out by extrusion or co-extrusion.
    Step 3) is generally carried out at ambient temperature since the geopolymerization takes place at ambient temperature.
    The invention will be better understood, and other objects, details, characteristics and advantages thereof will appear more clearly during the following description of particular embodiments of the invention, given only by way of illustration and not limitation, with reference to the appended figures.
    In these figures:
    - Figure 1 is a schematic sectional view in cross section of an electric cable of the prior art not according to the invention;
    - Figure 2 is a schematic sectional view in cross section of an electric cable according to an embodiment of the present invention.
    For reasons of clarity, only the essential elements for the understanding of the invention have been represented schematically in these figures, and this without respecting the scale.
    The electric cable 10, illustrated in FIG. 1, corresponds to a fire-resistant medium-voltage electric cable of the SHXCHX type for marine type applications.
    This electric cable 10 comprises: an elongated central electrically conductive element 1 and, successively and coaxially around this central conductive element 1, an internal semiconductor screen 1.1, an electrically insulating layer 2 (eg made of crosslinked ethylene and propylene elastomer , EPR.), An external semiconductor screen 2.1, a semiconductor ribbon layer 3, a metal braid 4 (eg made of tinned copper wires of circular section), an internal sheath comprising a polyester ribbon 5 and wires of tinned copper 6, a polyester ribbon 7, and an external sheath 8 (eg of elastomer).
    The electric cable 11, illustrated in FIG. 2, corresponds to an electric cable with a structure similar to that of the cable in FIG. 1 but in which two composite layers as defined in the invention have been incorporated.
    This electrical cable 11 comprises: an elongated central electrically conductive element 1 and, successively and coaxially around this central conductive element 1, an internal semiconductor screen 1.1, an electrically insulating layer 2 (eg made of crosslinked ethylene and propylene elastomer , EPR.), An external semiconductor screen 2.1, a semiconductor ribbon layer 3, a metal braid 4 (eg made of tinned copper wires of circular section), a first composite layer 9 as defined in the invention , an internal sheath comprising a polyester ribbon 5 and tinned copper wires 6, a polyester ribbon 7, a second composite layer 9 as defined in the invention, and an external sheath 8 (eg made of elastomer).
    The following examples illustrate the present invention. They are not limiting on the overall scope of the invention as presented in the claims. The ratios between the oxides are molar ratios and the% indicated are by mass.
    EXAMPLES
    The raw materials used in the examples are listed below:
    - aqueous sodium silicate solution at around 50% by mass, of the “waterglass” type, Simalco, of formula Na 2 O.2SiO 2 and of SiO 2 / Na 2 O molar ratio of approximately 2,
    - aluminosilicate Aluminosilicate, PoleStar® 200R, Imerys, with an AI 2 O 3 / SiO 2 molar ratio of 41/55 (ie approximately 0.745),
    - running water,
    - sodium hydroxide, Sigma Aldrich, purity> 85%,
    - carboxymethylcellulose, Aqualon ™, Ashland,
    - glycerol, 8400, Roquette.
    Unless otherwise indicated, all these raw materials were used as received from the manufacturers.
    Example 1: Preparation of a fire-resistant device according to the invention
    An alkali silicate solution was prepared by mixing 252 g of an aqueous sodium silicate solution, 276 g of water and 54 g of sodium hydroxide. Then 288 g of aluminosilicate were mixed with the alkali silicate solution to form an aluminosilicate geopolymer composition.
    Said aluminosilicate geopolymer composition therefore included:
    - 14.5% by mass of sodium silicate,
    - 6.2% by mass of sodium hydroxide,
    - 33.1% by mass of aluminosilicate, and
    - 46.2% by mass of water.
    The aluminosilicate geopolymer composition comprised approximately 53.8% by mass of solid matter relative to the total mass of said composition.
    Separately, a solution of cellulose derivative was prepared by mixing 83.5 g of carboxymethylcellulose (CMC) and 438.5 g of glycerol.
    The cellulose derivative solution was added to the aluminosilicate geopolymer composition to form a composite composition.
    The composite composition included 6.0% by mass of CMC, 31.5% by mass of glycerol, 20.7% by mass of aluminosilicate, 3.9% by mass of potassium hydroxide, 9.0% by mass sodium silicate and 28.9% by mass of water.
    The composite composition was extruded in the form of a ribbon using a MAPR.E extruder.
    The tape was approximately 3.5mm thick.
    权利要求:
    Claims (2)
    [1" id="c-fr-0001]
    1. Device comprising an energy and / or telecommunication cable, and / or an accessory for an energy and / or telecommunication cable, characterized in that said cable and / or said cable accessory comprises at least one composite layer obtained from a composite composition comprising at least one organic compound having a boiling or decomposition temperature greater than 100 ° C, at least one cellulose derivative, and at least one cement composition chosen from an aluminosilicate geopolymer composition and a magnesium composition comprising a magnesium silicate, an alkali silicate, water, and an alkaline base.
    2. Device according to claim 1, characterized in that the cement composition comprises water, silicon (Si), aluminum (Al) or magnesium (Mg), oxygen (O), and at least one element chosen from potassium (K), sodium (Na), lithium (Li), cesium (Cs), and calcium (Ca).
    3. Device according to claim 1 or 2, characterized in that the aluminosilicate geopolymer composition comprises an alkali silicate, an aluminosilicate, water, and optionally an alkaline base.
    4. Device according to any one of the preceding claims, characterized in that the aluminosilicate geopolymer composition comprises from 10 to 50% by mass of an aluminosilicate, from 8 to 35% by mass of an alkali silicate, from 0 to 10 % by mass of an alkaline base and from 10 to 55% by mass of water.
    5. Device according to any one of the preceding claims, characterized in that the magnesium-based composition comprises from 10 to 50% by mass of an aluminosilicate, from 8 to 35% by mass of an alkali silicate, from 5 to 20% by mass of an alkaline base and from 10 to 55% by mass of water.
    6. Device according to any one of the preceding claims, characterized in that the cement composition represents from 30 to 80% by mass, relative to the total mass of the composite composition.
    7. Device according to any one of the preceding claims, characterized in that the cellulose derivative is a cellulose ether or a cellulose ester.
    8. Device according to any one of the preceding claims, characterized in that the cellulose derivative represents from 3 to 20% by mass, relative to the total mass of the composite composition.
    9. Device according to any one of the preceding claims, characterized in that the organic compound is chosen from polyols.
    10. Device according to any one of the preceding claims, characterized in that the organic compound represents from 15 to 50% by mass, relative to the total mass of the composite composition.
    11. Device according to any one of the preceding claims, characterized in that the composite composition further comprises one or more additives chosen from starch, a plasticizer, an inert filler, a dye, an organic additive with a polymer structure, a crosslinking agent and one of their mixtures.
    12. Device according to any one of the preceding claims, characterized in that the composite layer of the invention is an extruded layer, a tape layer, or a layer in the form of a padding.
    13. Device according to any one of the preceding claims, characterized in that the composite layer has a thickness ranging from 2 to 6 mm.
    14. Device according to any one of the preceding claims, characterized in that the composite layer is an internal layer of said cable or of said cable accessory.
    15. Method for manufacturing a device as defined in any one of the preceding claims, characterized in that it comprises at least the following steps:
    1) the preparation of a composite composition according to at least the following steps:
    TJ
    1) the preparation of a cementitious composition chosen from an aluminosilicate geopolymer composition comprising an aluminosilicate, an alkaline silicate, water, and optionally an alkaline base, and a magnesium-based composition comprising a magnesium silicate, a
    5 alkali silicate, water, and an alkaline base, ii) mixing the cement composition of step i) with a cellulose derivative, an organic compound having a boiling or decomposition temperature above 100 ° C approximately, and possibly water; and
    [2" id="c-fr-0002]
    2) the formation of a composite layer from the composite composition obtained in step 1):
    - either around one or more elongated conductive elements and / or around a layer of an energy and / or telecommunication cable, when the device is a cable,
    - or around at least one of the layers of a junction or of a
    15 termination, when the device is a cable accessory.
    类似技术:
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    同族专利:
    公开号 | 公开日
    US10961156B2|2021-03-30|
    US20190202739A1|2019-07-04|
    KR20190074241A|2019-06-27|
    CN110010285A|2019-07-12|
    EP3503121A1|2019-06-26|
    FR3075453B1|2019-12-13|
    ES2834935T3|2021-06-21|
    EP3503121B1|2020-09-09|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB454461A|1934-09-08|1936-10-01|British Thomson Houston Co Ltd|Improved insulating and protective covering for electric cables|
    US20140026787A1|2012-07-25|2014-01-30|Council Of Scientific & Industrial Research|Composition for advanced hybrid geopolymeric functional materials and a process for the preparation thereof|
    WO2016092200A1|2014-12-10|2016-06-16|Nexans|Cable or cable accessory comprising a fire-resistant layer|
    WO2017098114A1|2015-12-11|2017-06-15|Nexans|Fire-resistant cable|
    NZ527772A|2003-08-22|2005-10-28|Ind Res Ltd|Alkali activated fly ash based geopolymer cements and methods for their production|
    CN101272985A|2005-07-26|2008-09-24|伊尼奥斯硅石有限公司|Aqueous aluminosilicate gel-forming composition|
    NL1033269C2|2007-01-23|2008-07-24|Ertecee B V|Aqueous gel-forming composition, e.g. as fire retardant coating to substrate, comprises aluminosilicate and organic liquid, where aluminosilicate comprises alkali metal aluminate and alkali metal silicate each having specified molar ratio|
    CN104761884A|2009-06-08|2015-07-08|亨茨曼国际有限公司|Flame retardant thermoplastic composition|
    FR2949227B1|2009-08-21|2013-09-27|Laboratoire Central Des Ponts Et Chaussees|GEOPOLYMERIC CEMENT AND USE THEREOF|
    WO2013044325A1|2011-09-30|2013-04-04|Hyssil Pty Ltd|Geopolymer product|
    ES2581906T3|2012-03-30|2016-09-08|Dow Global Technologies Llc|Fire resistant composite structure|
    FR3026899B1|2014-10-03|2016-10-28|Nexans|FIRE RESISTANT CABLES CONNECTION|FR3087574B1|2018-10-18|2021-06-25|Nexans|LOW VOLTAGE CABLE BLOCKING LAYER WITH IMPROVED FIRE PROTECTION|
    CN110372354A|2019-08-26|2019-10-25|福建省德化县天俊陶瓷有限公司|A kind of high white pottery porcelain and preparation method thereof|
    CN111540525A|2020-05-26|2020-08-14|安徽太平洋电缆股份有限公司|Heat-insulating bottle type B1-grade light fireproof cable|
    CN112700920B|2020-12-16|2022-02-22|新疆胡杨线缆制造有限公司|Self-adaptive rigid-flexible dual-state fireproof cable|
    法律状态:
    2018-12-20| PLFP| Fee payment|Year of fee payment: 2 |
    2019-06-21| PLSC| Search report ready|Effective date: 20190621 |
    2019-12-19| PLFP| Fee payment|Year of fee payment: 3 |
    2020-12-23| PLFP| Fee payment|Year of fee payment: 4 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1762516A|FR3075453B1|2017-12-19|2017-12-19|DEVICE COMPRISING A CABLE OR A CABLE ACCESSORY CONTAINING A FIRE RESISTANT COMPOSITE LAYER|
    FR1762516|2017-12-19|FR1762516A| FR3075453B1|2017-12-19|2017-12-19|DEVICE COMPRISING A CABLE OR A CABLE ACCESSORY CONTAINING A FIRE RESISTANT COMPOSITE LAYER|
    EP18212568.2A| EP3503121B1|2017-12-19|2018-12-14|Device comprising a cable or a cable accessory containing a fire-resistant composite layer|
    ES18212568T| ES2834935T3|2017-12-19|2018-12-14|Device comprising a cable or cable accessory containing a layer of fire-resistant composite material|
    KR1020180164155A| KR20190074241A|2017-12-19|2018-12-18|Device comprising a cable or a cable accessory containing a fire-resistant composite layer|
    US16/224,339| US10961156B2|2017-12-19|2018-12-18|Device comprising a cable or a cable accessory containing a fire-resistant composite layer|
    CN201811555667.2A| CN110010285A|2017-12-19|2018-12-19|Equipment including cable or cable accessory with fire resisting composite layer|
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