EP4168621A1 - Method for manufacturing a fire-resistant and/or fire-retardant cable - Google Patents

Method for manufacturing a fire-resistant and/or fire-retardant cable

Info

Publication number
EP4168621A1
EP4168621A1 EP21740129.8A EP21740129A EP4168621A1 EP 4168621 A1 EP4168621 A1 EP 4168621A1 EP 21740129 A EP21740129 A EP 21740129A EP 4168621 A1 EP4168621 A1 EP 4168621A1
Authority
EP
European Patent Office
Prior art keywords
fibrous material
composition
cable
carried out
approximately
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21740129.8A
Other languages
German (de)
French (fr)
Inventor
Thierry Auvray
Franck Gyppaz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nexans SA
Original Assignee
Nexans SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nexans SA filed Critical Nexans SA
Publication of EP4168621A1 publication Critical patent/EP4168621A1/en
Pending legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/0048—Fibrous materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C04B22/12—Acids or salts thereof containing halogen in the anion
    • C04B22/124—Chlorides of ammonium or of the alkali or alkaline earth metals, e.g. calcium chloride
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/38—Polysaccharides or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/006—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mineral polymers, e.g. geopolymers of the Davidovits type
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D06M15/05—Cellulose or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D06M15/11—Starch or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D06M15/13—Alginic acid or derivatives thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/22—Sheathing; Armouring; Screening; Applying other protective layers
    • 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
    • H01B3/12—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances ceramics
    • 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
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/48—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances fibrous materials
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00612—Uses not provided for elsewhere in C04B2111/00 as one or more layers of a layered structure
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/30—Flame or heat resistance, fire retardancy properties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2400/00—Specific information on the treatment or the process itself not provided in D06M23/00-D06M23/18
    • D06M2400/02—Treating compositions in the form of solgel or aerogel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding

Definitions

  • the present invention relates to a method of manufacturing a cable using the impregnation of a nonwoven fibrous material with a liquid geopolymer composition and the addition of at least one precursor composition of a gel to the liquid geopolymer composition. .
  • retardant and / or fire-resistant cables intended for energy transport and / or data transmission such as retardant and / or resistant electrical and / or optical security cables.
  • fire in particular halogen-free, capable of operating for a given period of time under fire conditions without being a fire propagator or generating significant smoke.
  • These safety cables are in particular medium voltage power transmission cables (especially 6 to 45-60 kV) or low frequency transmission cables, such as control or signal cables.
  • a method of manufacturing a fire resistant cable comprising the following steps: a step of preparing a geopolymer composition comprising a sodium silicate, water, potassium hydroxide, an aluminosilicate, and polypropylene fibers; a step of winding a tape of non-woven paper around an assembly of copper conductors, a step of impregnation by dipping and coating of the assembly of copper conductors / non-woven paper tape, in the geopolymer composition previously prepared, to form a composite layer surrounding the copper conductors, followed by a step of hot extrusion of a protective polymer sheath.
  • the process is long, in particular due to the drying step, and cannot be carried out continuously.
  • the constituent elements of the cable near the composite layer based on a geopolymer material can easily be contaminated by the geopolymer composition and / or stick to said composite layer, which is not desired.
  • An object of the invention is to overcome all or part of the aforementioned drawbacks, and to provide a method of manufacturing a fire retardant cable, said method being easy to implement, in particular easily industrializable, economical and rapid, and making it possible to lead to a cable with good mechanical properties, especially in terms of flexibility and durability.
  • the first object of the invention is a method of manufacturing a cable comprising at least one elongated electrically conductive element and at least one composite layer surrounding said elongated electrically conductive element, characterized in that it comprises at least the following steps: i ) impregnating a nonwoven fibrous material, preferably in the form of a sliver or strip, with a liquid geopolymer composition, and ii) forming a gel encapsulating or supporting said nonwoven fibrous material, said gel comprising a geopolymer material , and in that said method further comprises a step a) of adding a gelling composition to the liquid geopolymer composition, to form said gel during step ii).
  • the method of the invention is rapid, easy to implement, in particular from an industrial and economic point of view, and it guarantees the production of a fire resistant and / or retardant cable having good mechanical properties, in particular in terms of flexibility and durability. Furthermore, the method of the invention makes it possible to protect the composite layer, and in particular to prevent the contamination of the constituent elements of the cable near the composite layer by the liquid geopolymer composition, or their bonding to said composite layer.
  • the inventors of the present application have observed that the presence of a gelling composition in the liquid geopolymer composition makes it possible to reduce the release of water over time, and in particular during the process, which is detrimental for the manufacture of the liquid. cable.
  • the liquid geopolymer composition used in step i) is preferably a liquid geopolymer composition at room temperature, i.e. at a temperature ranging from 18 to 25 ° C approximately.
  • the liquid geopolymer composition from step i) is preferably a liquid aluminosilicate geopolymer composition.
  • the liquid geopolymer composition of the invention is particularly preferably a liquid geopolymer composition comprising 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).
  • the liquid geopolymer composition can in particular comprise at least a first aluminosilicate, at least a first alkali silicate, water, and optionally an alkaline base.
  • the liquid geopolymer composition is a precursor composition of a geopolymer.
  • it comprises ingredients (first aluminosilicate, at least a first alkali silicate, water, and optionally an alkaline base; or first metakaolin, second metakaolin, first alkali silicate, water, and optionally an alkaline base and / or a second alkali silicate as defined below) which geopolymerize together (by polycondensation) to form a geopolymer also called geopolymer material as defined in the invention.
  • the first aluminosilicate can be chosen from metakaolins (ie calcined kaolins), fly ash (well known under the anglicism "fly ash”), blast furnace slag (well known by the anglicism "blast furnace slag”), swelling clays such as bentonite, calcined clays, any type of compound comprising aluminum and silica fume, zeolites, and a mixture thereof.
  • metakaolins ie calcined kaolins
  • fly ash well known under the anglicism "fly ash”
  • blast furnace slag well known by the anglicism "blast furnace slag”
  • swelling clays such as bentonite, calcined clays, any type of compound comprising aluminum and silica fume, zeolites, and a mixture thereof.
  • metakaolins are preferred, in particular those marketed by the company Imérys.
  • the expression “metakaolin” means a calcined kaolin or a dehydroxylated aluminosilicate. It is preferably obtained by dehydration of a kaolin or of a kaolinite. This dehydration is conventionally obtained by calcination.
  • the liquid geopolymer composition may comprise from 5 to 50% by weight approximately of aluminosilicate, and preferably from 10 to 35% by weight approximately of aluminosilicate, relative to the total weight of the liquid geopolymer composition.
  • the liquid geopolymer composition may further comprise a second aluminosilicate different from the first aluminosilicate.
  • the liquid geopolymer composition comprises two calcined kaolins having different calcination temperatures.
  • the liquid geopolymer composition comprises a first metakaolin chosen from kaolins calcined at a temperature T ci of at least 650 ° C approximately, and a second metakaolin chosen from kaolins calcined at a temperature temperature T C 2 such that T C 2 - T ci > 100 ° C approximately, at least a first alkali metal silicate, water, and optionally an alkaline base.
  • the liquid geopolymer composition can then exhibit improved mechanical properties, in particular in terms of flexibility and durability, while ensuring good reaction and fire resistance properties.
  • the second metakaolin being chosen from kaolins calcined at a temperature T C 2 such as T C 2 - T ci > 100 ° C approximately, it is different from the first metakaolin as defined in the invention.
  • the first metakaolin is a kaolin calcined at a temperature T ci of at least approximately 700 ° C, and preferably of at least 725 ° C approximately.
  • the first metakaolin is a kaolin calcined at a temperature T ci of at most 875 ° C approximately, and preferably at most 825 ° C approximately.
  • the first metakaolin can comprise at least 20 mol% approximately, and preferably at least 30 mol% approximately, of aluminum oxide (Al2O3), relative to the total number of moles of the first metakaolin.
  • Al2O3 aluminum oxide
  • the first metakaolin may comprise at most 60 mol% approximately, and preferably at most 50 mol% approximately, of aluminum oxide (Al2O3), relative to the total number of moles of the first metakaolin.
  • the first metakaolin may comprise at least 35 mol% approximately, and preferably at least 45 mol% approximately, of silicon oxide (S1O2), relative to the total number of moles of the first metakaolin.
  • the first metakaolin may comprise at most 75 mol% approximately, and preferably at most 65 mol% approximately, of silicon oxide (S1O2), relative to the total number of moles of the first metakaolin.
  • the metakaolins sold by the company Imérys, in particular that marketed under the reference PoleStar ® 450.
  • the first metakaolin can be chosen from kaolins calcined at T ci as defined in the invention, for at least approximately 1 min, preferably for at least approximately 10 min, particularly preferably for a period ranging from approximately 30 min. at 8 h, and more particularly preferably for a period ranging from approximately 2 h to 6 h.
  • the second metakaolin is preferably chosen from kaolins calcined at a temperature T C 2 such that T C 2 - T ci > 150 ° C approximately, particularly preferably such that T C 2 - T ci > 200 ° C approximately, and more particularly preferably such that T C 2 - T ci > 250 ° C approximately.
  • the second metakaolin is a kaolin calcined at a temperature T C 2 of at least 800 ° C approximately, preferably at least 850 ° C approximately, and particularly preferably of at least about 900 ° C.
  • the second metakaolin is a kaolin calcined at a temperature T C 2 of at most 1200 ° C approximately, and preferably at most 1150 ° C approximately.
  • the second metakaolin can comprise at least 20 mol% approximately, and preferably at least 30 mol% approximately, of aluminum oxide (Al 2 O 3 ), relative to the total number of moles of the second metakaolin.
  • the second metakaolin can comprise at most 60 mol% approximately, and preferably at most 50 mol% approximately, of aluminum oxide (Al2O3), relative to the total number of moles of the second metakaolin.
  • the second metakaolin can comprise at least 35 mol% approximately, and preferably at least 45 mol% approximately of silicon oxide (S1O2), relative to the total number of moles of the second metakaolin.
  • the second metakaolin can comprise at most 75 mol% approximately, and preferably at most 65 mol% approximately of silicon oxide (S1O2), relative to the total number of moles of the second metakaolin.
  • second metakaolin examples include metakaolins sold by Imérys society, especially that marketed under the reference PoleStar ® 200R.
  • the second metakaolin can be chosen from kaolins calcined at T C 2 as defined in the invention, for at least approximately 1 min, preferably for at least approximately 5 min, particularly preferably for a period ranging from approximately 10 min to 2 h, and more particularly preferably for a period ranging from approximately 15 min to 1 h.
  • the mass ratio [first metakaolin / second metakaolin] in the liquid geopolymer composition is preferably from 0.1 to 2 approximately, particularly preferably from 0.5 to 1.0 approximately, and more particularly preferably is approximately 1.
  • the liquid geopolymer composition can comprise from 5 to 50% by weight approximately, and preferably from 10 to 35% by weight approximately of first and second metakaolins, relative to the total weight of the liquid geopolymer composition.
  • the first and second metakaolins can be analyzed by differential thermal analysis (DTA) [absence or presence of a crystallization point or peak], nuclear magnetic resonance (NMR) [ 27 Al NMR spectrum], and / or X-ray diffraction ( DRX).
  • DTA differential thermal analysis
  • NMR nuclear magnetic resonance
  • DRX X-ray diffraction
  • the first metakaolin preferably exhibits a crystallization peak by differential thermal analysis, particularly preferably at a temperature ranging from 900 to 1060 ° C, and more particularly preferably at a temperature ranging from 950 to 1010 ° C.
  • the second metakaolin preferably comprises mullite.
  • the first alkali silicate can be chosen from sodium silicates, potassium silicates, and one of their mixtures.
  • the alkali metal silicates marketed by the company Silmaco or by the company PQ corporation are preferred.
  • the first alkali silicate is preferably sodium silicate.
  • the first alkali silicate may have an S1O2 / M2O molar ratio ranging from about 1.1 to about 35, preferably from about 1.3 to 10, and particularly preferably from about 1.4 to 5, with M being an atom of sodium or potassium, and preferably a sodium atom.
  • the liquid geopolymer composition can comprise from 5 to 60% by weight approximately, and preferably from 10 to 50% by weight approximately of first alkali silicate, relative to the total weight of the liquid geopolymer composition.
  • the liquid geopolymer composition may further comprise a second alkali silicate different from the first alkali silicate.
  • the second alkali silicate can be chosen from sodium silicates, potassium silicates, and one of their mixtures.
  • the alkali metal silicates marketed by the company Silmaco or by the company PQ Corporation are preferred.
  • the second alkali silicate is preferably sodium silicate.
  • the first and second alkali silicates can have respectively SÎ0 2 / M 2 0 and SiC / M 2 O molar ratios such as M and M ', which are identical, are chosen from a sodium atom and a potassium atom, and preferably a sodium atom, and said ratios have different values, preferably values such that their difference is at least 0.3, particularly preferably such that their difference is at least 0.5, and more particularly preferred such that their difference is at least 1.0.
  • the liquid geopolymer composition comprises:
  • a first alkali silicate having a molar ratio SÎO2 / M20 ranging from 1.5 to 2.6 approximately
  • a second alkali silicate having an SiO 2 / M'20 molar ratio greater than 2.6, preferably ranging from 2.8 to 4.5 approximately, and particularly preferably ranging from 3.0 to 4.0 approximately, being understood that M 'is identical to M.
  • the liquid geopolymer composition can comprise from 10 to 60% by weight approximately, and preferably from 20 to 50% by weight approximately of first and second alkali silicates, relative to the total weight of the liquid geopolymer composition.
  • the mass ratio [first alkali silicate / second alkali silicate] in the liquid geopolymer composition preferably ranges from 0.5 to 2.5, and particularly preferably from 0.8 to 2.0.
  • the alkaline base can be sodium hydroxide, or potassium hydroxide, and preferably sodium hydroxide.
  • the liquid geopolymer composition may be free from an alkaline base. This thus makes it possible to improve the handling of the liquid geopolymer composition, in particular during the preparation of a cable.
  • the solid matter / water mass ratio in said liquid geopolymer composition determines the solidification kinetics during step ii).
  • the liquid geopolymer composition may comprise from 35% to 80% by weight approximately, and more preferably from 40% to 70% by weight approximately, of solid materials (alkali silicate (s), aluminosilicate (s) and alkaline base), relative to the total weight of said liquid geopolymer composition.
  • solid materials alkali silicate (s), aluminosilicate (s) and alkaline base
  • the liquid geopolymer composition may further comprise one or more additives chosen from:
  • - mineral fibers in particular chosen from alumina or basalt fibers
  • a compound accelerating the setting in mass in particular chosen from aluminum sulphate, alums (eg double sulphate of aluminum and potassium), calcium chloride, calcium sulphate, hydrated calcium sulphate, sodium aluminate, sodium carbonate, sodium chloride, sodium silicate, sodium sulfate, iron (III) chloride, and sodium lignosulfonates,
  • an agent delaying setting in mass in particular chosen from ammonium, alkali metals, alkaline earth metals, borax, lignosulphonates and in particular metal salts of calcium lignosulphonates, sulphoalkylated lignins such as, for example, sulfomethylated lignin, hydroxycarboxylic acids, copolymers of salts of 2-acrylamido-2-methylpropane sulfonic acid and acrylic acid or maleic acid, and saturated salts,
  • an inert filler in particular chosen from talc, micas, dehydrated clays, and calcium carbonate,
  • the dye is preferably a liquid dye at room temperature (i.e. at 18-25 ° C).
  • the liquid geopolymer composition may comprise from 0.01 to 15% by weight approximately of additive (s), preferably from 0.1 to 8% by weight approximately of additive (s), and particularly preferably 0, 5 to 5% by weight approximately of additive (s), relative to the total weight of the liquid geopolymer composition.
  • the nonwoven fibrous material is preferably in the form of a ribbon or a strip.
  • the fibrous nonwoven material preferably has a soft and flexible structure.
  • the nonwoven fibrous material can be chosen from cellulosic materials, materials based on synthetic organic polymers, glass fibers, and a mixture thereof, and preferably from materials based on synthetic organic polymers.
  • the cellulosic materials can be chosen from paper, in particular blotting paper; non-woven materials made from functionalized or non-functionalized cellulose; structure matrices alveolar and / or fibrous made from natural fibers of cellulose acetate.
  • the materials based on synthetic organic polymers can be chosen from polymer materials with a porous and / or fibrous polyolefin (s) matrix, in particular those chosen from propylene homopolymers and copolymers, ethylene homopolymers and copolymers, high density polyethylenes (HDPE), aromatic polyamides (aramids), polyesters, and a mixture thereof.
  • s polyolefin
  • the nonwoven fibrous material is polyethylene terephthalate (PET).
  • the nonwoven fibrous material preferably has a basis weight ranging from 50 to 120 g / cm 2 approximately. This thus makes it possible to obtain a composite layer which is sufficiently flexible to be able to be handled easily, and sufficiently robust to obtain good fire protection.
  • Step i) can be carried out manually or automatically, and preferably automatically.
  • step i) is carried out at a speed ranging from 20 to 280 m / min approximately, and preferably ranging from 50 to 150 m / min approximately.
  • the impregnation step i) can be carried out on the nonwoven fibrous material alone (hereinafter referred to as the first variant), or on a nonwoven fibrous material / cable assembly comprising at least one elongate electrically conductive element (hereinafter referred to as second variant).
  • step i) is step i-vl) and it is preferably carried out by impregnation coating, and particularly preferably by pre-controlled coating.
  • Step i-vl) can for example be carried out using a coating device such as a coating die.
  • This device is particularly suitable for impregnating a nonwoven fibrous material alone, i.e. when it is not yet applied around the cable.
  • Step i-vl) is more particularly carried out by passing the nonwoven fibrous material through a coating device such as a die. coating, said device being supplied with the liquid geopolymer composition, in particular using means such as a pump. This thus makes it possible to directly distribute the desired amount of the liquid geopolymer composition homogeneously over the entire desired width of said nonwoven fibrous material.
  • Step i-vl) can in particular be a coating known according to the anglicism “tensioned web die coating”.
  • step i-vl) of impregnation is carried out at a temperature ranging from 15 ° C to 90 ° C approximately, and particularly preferably from 20 ° C to 40 ° C. about.
  • the nonwoven fibrous material may be placed on a dispenser such as an unwinder or unwinder, and said material may be dispensed or unwound continuously to implement at least step i)
  • step i-vl) is carried out by passing the nonwoven fibrous material through a coating device supplied with the liquid geopolymer composition at a flow rate D (in kg / min), the distributor delivers the nonwoven fibrous material at a speed V (in km / min), and the D / V ratio ranges from about 20 to 50 kg of liquid geopolymer composition / km of nonwoven fibrous material, and particularly preferably about 25 to 40 kg of liquid geopolymer composition / km of nonwoven fibrous material.
  • the amount of liquid geopolymer composition applied to the nonwoven fibrous material can thus be easily adjusted by a pump.
  • the speed V is preferably identical to the running speed of the cable.
  • the flow rate D can range from 0.5 kg / min to 4.5 kg / min approximately.
  • the speed V can range from approximately 20 m / min to 280 m / min, and preferably from 50 m / min to approximately 150 m / min.
  • step i) is step i-v2) and it is preferably carried out by coating soaking.
  • Step i-v2) can for example be carried out using an impregnation bath or tank comprising the liquid geopolymer composition into which is introduced the cable comprising at least one elongated electrically conductive element and a nonwoven fibrous material. surrounding said elongated electrically conductive member.
  • the bath or impregnation tank is preferably configured to allow passage of the cable comprising at least one elongated electrically conductive element and a nonwoven fibrous material surrounding said elongated electrically conductive element, through said impregnation bath.
  • the liquid geopolymer composition is then introduced into said impregnation bath, to allow step i-v2).
  • the bath or impregnation tank is preferably supplied with the liquid geopolymer composition, in particular using means such as a pump. This thus makes it possible to continuously supply said bath or tank with liquid geopolymer composition.
  • the impregnation step i-v2) is carried out at a temperature ranging from 15 ° C to 40 ° C approximately, and particularly preferably from 20 ° C to 30 ° C. about.
  • the speed V is preferably identical to the running speed of the cable.
  • step i-v2) is carried out by passing the cable comprising said elongated electrically conductive element and said nonwoven fibrous material surrounding said elongated electrically conductive element in an impregnation bath or tank supplied with the geopolymer composition. with a flow rate D (in kg / min).
  • the flow rate D can range from 0.5 kg / min to 4.5 kg / min approximately.
  • the cable running speed in step i-v2) can range from approximately 20 m / min to 280 m / min, and preferably from 50 m / min to approximately 150 m / min.
  • the nonwoven fibrous material impregnated with the liquid geopolymer composition (first variant) or the cable / nonwoven fibrous material assembly impregnated with the liquid geopolymer composition (first variant) is then directly used in step ii) or step a ) as defined in the invention.
  • Step a) of adding a gelling composition can be carried out before step i) or after step i) of impregnating the nonwoven fibrous material.
  • Step a) thus makes it possible to add to the liquid geopolymer composition alone (i.e. before step i)) or to the liquid geopolymer composition impregnating the nonwoven fibrous material (i.e. after step i)) the gelling composition.
  • the gelling composition is in other words a precursor composition of a gel or a composition capable of forming a gel, in particular when it is added to the liquid geopolymer composition.
  • the gelling composition can comprise at least one precursor compound of a gel chosen from crosslinkable organic polymers, polysaccharides, organic monomers, and one of their mixtures.
  • polysaccharides mention may be made of starches, modified starches, alginates, modified alginates, chitosan, hyaluronic acid, carrageenans, polysaccharide gums such as agar-agar, xanthan gum or gellan gum , pectins, cellulose, cellulose derivatives, modified dextrans, and hyaluronic acid.
  • the polysaccharide used is in the form of a powder.
  • crosslinkable organic polymers mention may be made of polyorganosiloxanes and poly (meth) acrylates.
  • organic monomers mention may be made of acrylates, methacrylates and acrylamides.
  • the gelling composition may further comprise a crosslinking agent and / or a crosslinking catalyst and / or an initiator, in particular when the precursor compound of a gel is chosen from crosslinkable organic polymers and organic monomers.
  • the gelling composition may further comprise one or more viscosity agents (ie which increases the viscosity of said composition), such as, for example, calcium chloride, calcium carbonate, or a mixture thereof, in particular when the precursor compound d a gel is chosen from polysaccharides, and in particular alginates.
  • the viscosity agent is preferably soluble in the gelling composition at a temperature ranging from 15 to 40 ° C approximately.
  • the precursor compound of a gel is preferably chosen from polysaccharides, and particularly preferably from alginates and starches, and more particularly preferably in the form of a powder.
  • Step a) is preferably carried out after step i).
  • the addition of the gelling composition a) can be carried out by spraying a powder of the gelling composition onto the liquid geopolymer composition; or by mixing a liquid gelling composition with the liquid geopolymer composition.
  • Spraying a powder of the gelling composition onto the liquid geopolymer composition is preferred.
  • the nonwoven material impregnated with the geopolymer composition can for example pass into a spray cell comprising a tubular chamber and nozzles allowing the spraying of the gelling composition on the fibrous material. impregnated nonwoven [steps a) and ii)].
  • the spray cell can be connected to a tightening device, in particular to allow the confinement of the gel / nonwoven material assembly around the elongated electrically conductive element when the second variant is used for step iii) described below. after.
  • Step ii) forming a gel encapsulating the nonwoven fibrous material
  • Step ii) makes it possible to bring the liquid geopolymer composition from a liquid state to a gel state linked to the presence of a gelling composition.
  • Step ii) can be concomitant with step a).
  • the addition of the gelling composition to the liquid geopolymer composition makes it possible to directly form a gel encapsulating the nonwoven material.
  • Step ii) can be carried out after step a).
  • step ii) is carried out in the presence of an external stimulus, such as temperature or the presence of UV rays, for example to trigger crosslinking.
  • a gel encapsulating the nonwoven fibrous material is formed, said gel comprising a geopolymer material. This thus makes it possible to pump part of the excess water and / or to dry at least on the surface the whole non-woven fibrous material / polymer material, and thus to obtain a composite layer whose mechanical properties are retained over time. .
  • this gelling composition a chemical or physical, volume or surface network is obtained during step ii) which keeps the nonwoven fibrous material in place and / or encapsulates it and / or plays the role of support; while protecting the composite layer obtained from water loss over time.
  • the method preferably does not include a drying step, in particular due to the presence of step ii).
  • the gel can make it possible to ensure surface gelation, thus providing at the end of step ii) a texture that is dry to the touch after fixing of the water.
  • the method may further comprise, before step i), a step i 0 ) of preparing the liquid geopolymer composition.
  • Step io) is generally carried out at a high pH, in particular varying from 10 to 13.
  • Step io) preferably comprises the following sub-steps:
  • the aqueous solution of the first alkali silicate can be prepared by mixing silicon dioxide S1O2 or an alkali silicate with an MOH base in which M is K or Na.
  • the silicon dioxide S1O2 can be chosen from silica fume (ie fumed silica), quartz, and mixtures thereof.
  • Sub-step ioi) can be carried out by dissolving the alkaline base in water, causing the release of heat (exothermic reaction), then adding the silica (or the alkali silicate). The heat released then accelerates the dissolution of the silica (or of the alkali silicate) during the sub-step ioi), and of the first aluminosilicate during the sub-step 102).
  • step io) of preparing the liquid geopolymer composition may comprise mixing said first aluminosilicate (of preferably in powder form) and optionally said second aluminosilicate (preferably in powder form), with said first alkali silicate (preferably in the form of an aqueous solution), and optionally said second alkali silicate (preferably in the form of an aqueous solution).
  • Step io) preferably comprises mixing the first and second metakaolins, with the first alkali silicate and optionally the second alkali silicate, water, and optionally an alkaline base.
  • the first and second metakaolins and the first and second alkali silicates are as defined in the invention.
  • step io) comprises the following sub-steps: ioa) the mixture of the first and second alkali metal silicates, preferably in the form of aqueous solutions, in particular with stirring, iob) optionally the addition of an alkaline base, in particular while maintaining the agitation, and ioc) the addition of the first and second metakaolins, preferably in the form of powders, in particular while maintaining the agitation.
  • a fluid and homogeneous solution is preferably obtained.
  • the geopolymer composition can comprise from 35% to 80% by weight approximately, and particularly preferably from 40% to 70% by weight approximately, of solid materials (alkali silicate (s) , aluminosilicate (s), and alkaline base), relative to the total weight of said liquid geopolymer composition.
  • solid materials alkali silicate (s) , aluminosilicate (s), and alkaline base
  • Such a mass ratio makes it possible to have a liquid geopolymer composition that is fluid enough to allow it to be handled, and the solidification kinetics of which are slow enough to allow the formation of a composite cable layer as defined below.
  • the solid matter / water mass ratio in said liquid geopolymer composition can make it possible to determine the solidification kinetics of said liquid geopolymer composition.
  • Step io) is preferably carried out at ambient temperature (approximately 18-25 ° C.).
  • the method may further comprise a step iii) of applying the nonwoven fibrous material around a cable comprising at least one elongated electrically conductive element.
  • Step iii) can be carried out either after impregnation step i), when the latter uses the nonwoven fibrous material alone [first variant of the invention or step i-vl)], or before the impregnation step i), when the latter uses the cord / nonwoven fibrous material assembly [second variant of the invention or step i-v2)].
  • step iii) is then a step iii-vl).
  • Step iii-vl) is preferably carried out after step ii) as defined in the invention.
  • the nonwoven fibrous material alone is impregnated with the liquid geopolymer composition according to step i), a gel is formed according to step ii), then the gel / nonwoven fibrous material assembly is applied around the element. electrically conductive elongated according to step iii-vl).
  • the fibrous nonwoven material is in the form of a web or ribbon. This thus makes it possible to facilitate step iii-vl).
  • the gel / nonwoven fibrous material assembly can be applied either directly around one or more elongated conductive elements, or around an internal layer of said cable which is itself around one or more elongated conductive elements.
  • the application step iii-vl) can be carried out by winding the tape or the tape around the cable.
  • the winding can be longitudinal (i.e. along the longitudinal axis of the cable or in other words in the direction of the length of the cable) or helical, and preferably longitudinal.
  • the longitudinal winding can also be carried out with overlap zones, the overlap zone (s) representing from 10 to 20% approximately.
  • Step iii-vl) can be carried out manually or in an automated fashion, and preferably in an automated fashion.
  • Step iii-vl) can be carried out by passing the gel / nonwoven fibrous material assembly of step ii) through a tightening device or a shaping device (also by the terms “trumpet” or “ tape shaper ”).
  • the cable comprising at least one elongated electrically conductive element also passes through the tightening device during step iii-vl).
  • This device is a mechanical device which continuously wraps the gel / nonwoven fibrous material assembly around the elongated electrically conductive element. This thus makes it possible to facilitate the longitudinal winding of the gel / ribbon assembly around the cable.
  • Step iii-vl) is preferably carried out at ambient temperature (approximately 18-25 ° C.).
  • step iii) is then a step iii-v2).
  • Step iii-v2) is preferably carried out before step i) as defined in the invention.
  • the nonwoven fibrous material alone is first applied around the elongated electrically conductive element according to step iii-v2), then the cable / nonwoven material assembly is impregnated with the liquid geopolymer composition according to step i), and a gel is formed according to step ii).
  • Step iii-v2) allows the application of the nonwoven material around the elongated electrically conductive element, in particular to form a cable comprising at least one elongated electrically conductive element and a nonwoven fibrous material surrounding said elongate electrically conductive element.
  • the nonwoven fibrous material may be placed on a dispenser such as an unwinder or unwinder, and said material may be dispensed or unwound continuously in order to implement at least step iii-v2).
  • step iii-v2) the distributor delivers the nonwoven fibrous material at a speed V (in km / min).
  • the speed V is preferably identical to the running speed of the cable.
  • the speed V can range from approximately 20 m / min to 280 m / min, and preferably from 50 m / min to approximately 150 m / min.
  • the fibrous nonwoven material is in the form of a web or ribbon. This thus makes it possible to facilitate step iii-v2).
  • the nonwoven fibrous material can be applied either directly around one or more elongated conductive elements, or around an inner layer of said cable which is itself around one or more elongated conductive elements.
  • the application step iii-v2) can be carried out by winding the tape around the cable.
  • the winding can be longitudinal (ie along the longitudinal axis of the cable or in other words in the direction of the length of the cable) or helical, and preferably longitudinal.
  • the longitudinal winding makes it possible to reduce the production cost of the cable.
  • the longitudinal winding can also be carried out with overlap zones, the overlap zone (s) representing from 10 to 20% approximately.
  • Step iii-v2) can be performed manually or automatically, and preferably automatically.
  • Step iii-v2) can be implemented by passing the tape through a tightening device or a shaping device (also designated by the terms “trumpet” or “tape shaper”).
  • the cable comprising at least one elongated electrically conductive element also passes through the tightening device during step iii-v2).
  • This device is a mechanical device which continuously wraps the tape around the elongated electrically conductive element. This thus makes it possible to facilitate the longitudinal winding of the tape around the cable.
  • Step iii-v2) is preferably carried out at ambient temperature (approximately 18-25 ° C.).
  • the second variant is preferred.
  • the method may further comprise after step ii) or step iii-vl), a step iv) of applying a protective outer sheath around the composite layer.
  • the outer protective sheath can ensure the mechanical integrity of the cable.
  • the cable can then comprise at least one elongated electrically conductive element, the composite layer surrounding said elongated electrically conductive element, and at least one protective outer sheath surrounding said composite layer.
  • Step iv) is preferably carried out by extrusion, in particular at a temperature ranging from 140 ° C to 195 ° C approximately.
  • Step iv) can be carried out using an extruder.
  • an extrusion head can be positioned at the outlet of the shaping device as defined in the invention.
  • the protective outer sheath is preferably the outermost layer of the cable.
  • the outer protective sheath is preferably an electrically insulating layer.
  • the protective outer sheath is preferably made of a halogen-free material. It can be produced conventionally from materials retarding 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 type sheathing (for the anglicism “Halogen Free Flame Retardant”).
  • the outer protective sheath can comprise at least one organic or inorganic polymer.
  • organic or inorganic polymer is not limiting and these are well known to those skilled in the art.
  • the organic or inorganic polymer is chosen from crosslinked and noncrosslinked 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.
  • ethylene polymers such as 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, ethylene propylene diene monomer (EPDM) terpolymers or a mixture thereof.
  • LLDPE linear low density polyethylene
  • LDPE low density polyethylene
  • MDPE medium density polyethylene
  • HDPE high density polyethylene
  • EVA
  • the polymer of the outer protective sheath 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 one of theirs. mixtures.
  • the protective outer sheath may further include a hydrated flame retardant mineral filler.
  • This hydrated flame-retardant mineral filler acts mainly physically by decomposing endothermically (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.
  • endothermically e.g. release of water
  • the hydrated flame retardant inorganic filler can be a metal hydroxide such as magnesium hydroxide or aluminum trihydroxide.
  • the outer protective sheath may further comprise an inert filler, in particular chosen from talc, micas, dehydrated clays and one of their mixtures.
  • the composite layer is preferably an electrically insulating layer.
  • the term “electrically insulating layer” is understood to mean 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 25 ° C).
  • the composite layer is preferably a retardant and / or fire resistant layer.
  • the composite layer preferably has a thickness ranging from approximately 0.2 to 3 mm, and particularly preferably ranging from 0.5 to 1 mm approximately.
  • the composite layer of the invention is preferably a tape layer (ie in the form of a tape or a strip).
  • the composite layer preferably has a substantially constant thickness and in particular constitutes a continuous protective envelope.
  • the composite layer can in particular comprise 2 to 3 superimposed tapes.
  • the composite layer of the invention is preferably non-porous.
  • the composite layer is preferably an internal layer of said cable.
  • the term “internal layer” is understood to mean a layer which does not constitute the outermost layer of the cable.
  • the composite layer preferably comprises at least one geopolymeric material, a gel (in which the geopolymeric material is dispersed), and the nonwoven fibrous material as defined in the invention.
  • the geopolymer material is obtained from a liquid geopolymer composition as defined in the invention, preferably by curing, geopolymerization and / or polycondensation of said liquid geopolymer composition.
  • the liquid geopolymer composition as defined in the invention is suitable for forming said geopolymer material.
  • the ingredients of the liquid geopolymer composition can therefore undergo polycondensation to form said geopolymer material.
  • the hardening takes place by internal reaction of the polycondensation type. Hardening, for example, is not the result of simple drying, as is generally the case with binders based on alkali silicates.
  • geopolymer materials result from a reaction of mineral polycondensation 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 expression “geopolymer material” means a solid material comprising 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).
  • the geopolymer material can be an aluminosilicate geopolymer material.
  • the aluminosilicate geopolymer material can be chosen from the poly (sialates) corresponding to the formula (I) M n (-Si-0- Al-0-) n [(M) -PS] and having an equal Si / Al molar ratio to 1, the poly (sialate-siloxos) corresponding to the formula (II) M n (-Si-0AI-0Si-0) n [(M) -PPS] and having an Si / Al molar ratio equal to 2, the poly (sialate-disiloxos) corresponding to the formula (III) M n (-Si-0-Al-0-Si-0-Si-0) n [(M) -PSDS] and having an equal Si / Al molar ratio to 3, and other poly (sialates) of Si / Al ratio> 3, the aforementioned poly (sialates) comprising an alkali metal cation M chosen from K, Na, Li, Cs
  • the geopolymer material represents from 5 to 98% by weight approximately, preferably from 55 to 95% by weight approximately, and more preferably from 65 to 90% by weight approximately, relative to the total weight of the composite layer.
  • the nonwoven fibrous material represents from 2 to 95% by weight approximately, particularly preferably from 5 to 45% by weight approximately, and even more preferably from 10 to 35% by weight approximately, relative to the total weight of the composite layer.
  • the gel represents from 0.1 to 15% by weight approximately, particularly preferably from 1 to 10% by weight approximately, and even more preferably from 2 to 6% by weight approximately , relative to the total weight of the composite layer.
  • the cable obtained according to a process in accordance with the invention satisfies at least one of the standards for reaction or non-propagation to fire chosen from standards EN 60332-1, EN 60332-3, and EN 50399 (2012/02 + Al 2016); and preferably to standard EN 50399 (2012/02 + Al 2016), in particular the B2ca, sla, dO, al classification criteria of said standard, and possibly the EN 60332-1 and EN 60332-3 standards.
  • the cable is an energy and / or telecommunications cable, and preferably an electric cable.
  • the composite layer may then surround the plurality of elongate electrically conductive elements of the cable.
  • the cable can comprise a single composite layer as defined in the invention or a plurality of composite layers as defined in the invention.
  • the cable comprises a single composite layer, and more particularly preferably a single internal composite layer.
  • the cable obtained according to the method of the invention further comprises one or more layers interposed between the elongated electrically conductive element and the composite layer as defined in the invention.
  • These layers can include one or more polymer layers such as electrically insulating polymer layers.
  • the method further comprises, before step iii), one or more steps of applying one or more of the layers mentioned above, around the elongated electrically conductive element, of all of the layers. elongated electrically conductive elements, or around each of the elongated electrically conductive elements, depending on the type of cable desired.
  • the cable comprises:
  • each of said electrically conductive elements being surrounded by a polymer layer, in particular electrically insulating, to form a plurality of isolated electrically conductive elements,
  • a composite layer as defined in the invention surrounding said plurality of insulated electrically conductive elements, and an outer protective sheath, in particular electrically insulating, surrounding said composite layer.
  • the process according to the invention is preferably a continuous process.
  • at least steps i), ii) and a), and preferably at least steps iO), i), ii), a) and iii) are carried out continuously.
  • the expression “continuous process” means that the process is carried out on a single production line, and / or without stages of rest, collection, or recovery. In other words, in the process according to the invention, there are no intermediate stages of rest between the distribution of the nonwoven fibrous material and the recovery / obtaining of the final cord. More particularly, steps i), ii) and a), or steps iO), i), ii), a), and iii) are concomitant, ie steps i), ii) and a), or steps iO), i), ii), a), and iii) are implemented at the same time.
  • the nonwoven fibrous material may be placed on a dispenser such as an unwinder or unwinder, and said material may be dispensed or unwound continuously in order to carry out at least steps i) and iii).
  • the nonwoven fibrous material in the form of a ribbon delivered by the unwinder or unwinder passes into the tightening or shaping device through which a cable comprising at least one elongated electrically conductive element passes according to step iii- v2), then the cable thus obtained passes into the bath or impregnation tank comprising the geopolymer composition according to step i-v2), then the cable thus impregnated leaves the impregnation tank and enters the spray cell to put carrying out steps a) and ii), then the cable obtained passes through the tightening device before entering the extruder head, in order to allow the extrusion of the polymer sheath around the cable according to step iv) .
  • the distributor delivers the nonwoven fibrous material at a speed V (in km / min).
  • the speed V is preferably identical to the running speed of the cable.
  • the impregnation bath or tank is supplied with the geopolymer composition at a flow rate D (in kg / min).
  • the flow rate D can range from 0.5 kg / min to 4.5 kg / min approximately.
  • the cable running speed in the process ranges from approximately 20 m / min to 280 m / min, and preferably ranges from approximately 50 m / min to 150 m / min.
  • Figure 1 shows a schematic sectional view of an electric cable as obtained according to the process according to the invention.
  • FIG. 2 represents a schematic view of the method according to the invention according to one embodiment.
  • the 10A electric cable illustrated in figure 1, corresponds to a fire-resistant electric cable of type K25 or RZ1K.
  • This electric cable 10 comprises four elongated electrically conductive elements 1, each being insulated with an electrically insulating layer 200, and, successively and coaxially around these four isolated elongated electrically conductive elements (100, 200), a composite layer 3 as defined in the invention surrounding the four elongated insulated electrically conductive elements (100, 200), and an outer sheath 400 of the HFFR type surrounding the composite layer 300 as defined in the invention, and is advantageously in the form of a ribbon.
  • FIG. 2 a schematic view of the process according to the invention implemented continuously is illustrated.
  • a nonwoven fibrous material 1 in the form of a tape is placed on a winder 2, unwound and brought to a tightening device 3 through which a cable comprising at least one elongated electrically conductive element 4 (bare cable 4) runs, in order to allow the longitudinal winding of the tape 1 around the cable 4 [step iii-v2) ]
  • the cable obtained comprising the elongated electrically conductive element and said nonwoven fibrous material surrounding said elongated electrically conductive element 5 passes into an impregnation bath 6 comprising a geopolymer composition 7, in order to allow the impregnation of the non-fibrous material.
  • the impregnated cable 8 obtained then passes into a spraying cell 9 comprising a tubular chamber and pipes allowing the spraying of a gelling composition 1 0 comprising 10 g of an alginate and 1 g of calcium chloride on the impregnated cable 8 [ steps a) and ii)].
  • a gelling composition 1 0 comprising 10 g of an alginate and 1 g of calcium chloride on the impregnated cable 8 [ steps a) and ii)].
  • the cable obtained 1 1 enters a tightening device 1 2 connected to said tubular chamber and is brought to an extruder head 1 3, in order to allow the extrusion of the polymer sheath around the cable to form a sheathed cable 14 [step iv)].
  • the composite layer obtained is dry and can be deformed while retaining its cohesion without any tearing. Aging tests show that steps a) and ii) make it possible to retain the flexibility properties after prolonged temperature aging, unlike the implementation of a process without steps a) and ii). The fire properties are not altered since the fire tests according to standard EN50399 remain unchanged B2, si, dl.

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Abstract

The present invention relates to a method for manufacturing a cable implementing the impregnation of a non-woven fibrous material with a liquid geopolymer composition and the addition of at least one precursor composition of a gel to the liquid geopolymer composition.

Description

Procédé de fabrication d’un câble résistant et/ ou retardant au feu Manufacturing process of a fire resistant and / or retardant cable
La présente invention concerne un procédé de fabrication d'un câble mettant en oeuvre l'imprégnation d'un matériau fibreux non tissé par une composition géopolymère liquide et l'ajout d'au moins une composition précurseur d'un gel à la composition géopolymère liquide. The present invention relates to a method of manufacturing a cable using the impregnation of a nonwoven fibrous material with a liquid geopolymer composition and the addition of at least one precursor composition of a gel to the liquid geopolymer composition. .
Elle s'applique typiquement, mais non exclusivement, à des câbles retardants et/ou résistants au feu destinés au transport d’énergie et/ou à la transmission de donnée tels que des câbles électriques et/ou optiques de sécurité retardants et/ou résistants au feu, notamment sans halogène, susceptibles de fonctionner pendant un laps de temps donné dans des conditions d’incendie sans être pour autant propagateur d’incendie, ni générateur de fumées importantes. Ces câbles de sécurité sont en particulier des câbles de transport d’énergie moyenne tension (notamment de 6 à 45-60 kV) ou des câbles de transmission basse fréquence, tels que des câbles de contrôle ou de signalisation. It typically, but not exclusively, applies to retardant and / or fire-resistant cables intended for energy transport and / or data transmission such as retardant and / or resistant electrical and / or optical security cables. fire, in particular halogen-free, capable of operating for a given period of time under fire conditions without being a fire propagator or generating significant smoke. These safety cables are in particular medium voltage power transmission cables (especially 6 to 45-60 kV) or low frequency transmission cables, such as control or signal cables.
De WO 2016/099200 est connu un procédé de fabrication d'un câble résistant au feu comprenant les étapes suivantes : une étape de préparation d'une composition géopolymère comprenant un silicate de sodium, de l'eau, de l'hydroxyde de potassium, un aluminosilicate, et des fibres de polypropylène ; une étape d'enroulement d'un ruban de papier non tissé autour d'un assemblage de conducteurs en cuivre, une étape d'imprégnation par trempage enduction de l'assemblage conducteurs en cuivre/ruban de papier non tissé, dans la composition géopolymère précédemment préparée, pour former une couche composite entourant les conducteurs en cuivre, puis une étape d'extrusion à chaud d'une gaine protectrice polymère. Le procédé est long, notamment de par l'étape de séchage, et ne peut être réalisé en continu. Par ailleurs, les éléments constitutifs du câble à proximité de la couche composite à base d'un matériau géopolymère peuvent être facilement contaminés par la composition géopolymère et/ou coller à ladite couche composite ce qui n'est pas souhaité. From WO 2016/099200 is known a method of manufacturing a fire resistant cable comprising the following steps: a step of preparing a geopolymer composition comprising a sodium silicate, water, potassium hydroxide, an aluminosilicate, and polypropylene fibers; a step of winding a tape of non-woven paper around an assembly of copper conductors, a step of impregnation by dipping and coating of the assembly of copper conductors / non-woven paper tape, in the geopolymer composition previously prepared, to form a composite layer surrounding the copper conductors, followed by a step of hot extrusion of a protective polymer sheath. The process is long, in particular due to the drying step, and cannot be carried out continuously. Furthermore, the constituent elements of the cable near the composite layer based on a geopolymer material can easily be contaminated by the geopolymer composition and / or stick to said composite layer, which is not desired.
Un but de l'invention est de pallier tout ou partie des inconvénients précités, et de fournir un procédé de fabrication d'un câble retardant au feu ledit procédé étant facile à mettre en oeuvre, notamment facilement industrialisable, économique et rapide, et permettant de conduire à un câble présentant de bonnes propriétés mécaniques, notamment en termes de flexibilité et de durabilité. An object of the invention is to overcome all or part of the aforementioned drawbacks, and to provide a method of manufacturing a fire retardant cable, said method being easy to implement, in particular easily industrializable, economical and rapid, and making it possible to lead to a cable with good mechanical properties, especially in terms of flexibility and durability.
L'invention a pour premier objet un procédé de fabrication d'un câble comprenant au moins un élément électriquement conducteur allongé et au moins une couche composite entourant ledit élément électriquement conducteur allongé, caractérisé en ce qu'il comprend au moins les étapes suivantes : i) imprégner un matériau fibreux non tissé, de préférence sous la forme d'un ruban ou d'une bande, avec une composition géopolymère liquide, et ii) former un gel encapsulant ou supportant ledit matériau fibreux non tissé, ledit gel comprenant un matériau géopolymère, et en ce que ledit procédé comprend en outre une étape a) d'ajout d'une composition gélifiante à la composition géopolymère liquide, pour former ledit gel lors de l'étape ii). The first object of the invention is a method of manufacturing a cable comprising at least one elongated electrically conductive element and at least one composite layer surrounding said elongated electrically conductive element, characterized in that it comprises at least the following steps: i ) impregnating a nonwoven fibrous material, preferably in the form of a sliver or strip, with a liquid geopolymer composition, and ii) forming a gel encapsulating or supporting said nonwoven fibrous material, said gel comprising a geopolymer material , and in that said method further comprises a step a) of adding a gelling composition to the liquid geopolymer composition, to form said gel during step ii).
Le procédé de l'invention est rapide, facile à mettre en oeuvre, notamment sur le plan industriel, économique, et il garantit l'obtention d'un câble résistant et/ou retardant au feu présentant de bonnes propriétés mécaniques, notamment en termes de flexibilité et de durabilité. Par ailleurs, le procédé de l'invention permet de protéger la couche composite, et notamment d'éviter la contamination des éléments constitutifs du câble à proximité de la couche composite par la composition géopolymère liquide, ou leur collage à ladite couche composite. En particulier, les inventeurs de la présente demande ont observé que la présence d'une composition gélifiante dans la composition géopolymère liquide permet de diminuer la libération d'eau dans le temps, et notamment au cours du procédé, qui est néfaste pour la fabrication du câble. The method of the invention is rapid, easy to implement, in particular from an industrial and economic point of view, and it guarantees the production of a fire resistant and / or retardant cable having good mechanical properties, in particular in terms of flexibility and durability. Furthermore, the method of the invention makes it possible to protect the composite layer, and in particular to prevent the contamination of the constituent elements of the cable near the composite layer by the liquid geopolymer composition, or their bonding to said composite layer. In particular, the inventors of the present application have observed that the presence of a gelling composition in the liquid geopolymer composition makes it possible to reduce the release of water over time, and in particular during the process, which is detrimental for the manufacture of the liquid. cable.
Etape i) d'impréanation du matériau fibreux non tissé Step i) impregnation of the nonwoven fibrous material
La composition aéopolvmère liquide The liquid air-polymer composition
La composition géopolymère liquide utilisée à l'étape i) est de préférence une composition géopolymère liquide à température ambiante, i.e. à une température allant de 18 à 25°C environ. The liquid geopolymer composition used in step i) is preferably a liquid geopolymer composition at room temperature, i.e. at a temperature ranging from 18 to 25 ° C approximately.
La composition géopolymère liquide de l'étape i) est de préférence une composition géopolymère aluminosilicate liquide. La composition géopolymère liquide de l'invention est de façon particulièrement préférée une composition géopolymère liquide comprenant de l'eau, du silicium (Si), de l'aluminium (Al), de l'oxygène (O), et au moins un élément choisi parmi le potassium (K), le sodium (Na), le lithium (Li), le césium (Cs), et le calcium (Ca), et de préférence choisi parmi le potassium (K) et le sodium (Na). The liquid geopolymer composition from step i) is preferably a liquid aluminosilicate geopolymer composition. The liquid geopolymer composition of the invention is particularly preferably a liquid geopolymer composition comprising 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).
La composition géopolymère liquide peut en particulier comprendre au moins un premier aluminosilicate, au moins un premier silicate alcalin, de l'eau, et éventuellement une base alcaline. The liquid geopolymer composition can in particular comprise at least a first aluminosilicate, at least a first alkali silicate, water, and optionally an alkaline base.
Dans l'invention, la composition géopolymère liquide est une composition précurseur d'un géopolymère. En d'autres termes, elle comprend des ingrédients (premier aluminosilicate, au moins un premier silicate alcalin, de l'eau, et éventuellement une base alcaline ; ou premier métakaolin, deuxième métakaolin, premier silicate alcalin, eau, et éventuellement une base alcaline et/ou un deuxième silicate alcalin tels que définis ci-après) qui géopolymérisent ensemble (par polycondensation) pour former un géopolymère également dénommé matériau géopolymère tel que défini dans l'invention. In the invention, the liquid geopolymer composition is a precursor composition of a geopolymer. In other words, it comprises ingredients (first aluminosilicate, at least a first alkali silicate, water, and optionally an alkaline base; or first metakaolin, second metakaolin, first alkali silicate, water, and optionally an alkaline base and / or a second alkali silicate as defined below) which geopolymerize together (by polycondensation) to form a geopolymer also called geopolymer material as defined in the invention.
Le premier aluminosilicate The first aluminosilicate
Le premier aluminosilicate peut être choisi parmi les métakaolins (i.e. kaolins calcinés), les cendres volantes (bien connues sous l'anglicisme « fly ash »), le laitier de haut fourneau (bien connu sous l'anglicisme « blast furnace slag »), les argiles gonflantes telles que la bentonite, les argiles calcinées, tout type de composé comprenant de l'aluminium et de la fumée de silice, les zéolithes, et un de leurs mélanges. The first aluminosilicate can be chosen from metakaolins (ie calcined kaolins), fly ash (well known under the anglicism "fly ash"), blast furnace slag (well known by the anglicism "blast furnace slag"), swelling clays such as bentonite, calcined clays, any type of compound comprising aluminum and silica fume, zeolites, and a mixture thereof.
Parmi ces composés, les métakaolins sont préférés, notamment ceux commercialisés par la société Imérys. Among these compounds, metakaolins are preferred, in particular those marketed by the company Imérys.
Dans l'invention, l'expression « métakaolin » signifie un kaolin calciné ou un aluminosilicate déshydroxylé. Il est de préférence obtenu par déshydratation d'un kaolin ou d'une kaolinite. Cette déshydratation est classiquement obtenue par calcination. La composition géopolymère liquide peut comprendre de 5 à 50% en poids environ d'aluminosilicate, et de préférence de 10 à 35% en poids environ d'aluminosilicate, par rapport au poids total de la composition géopolymère liquide. In the invention, the expression “metakaolin” means a calcined kaolin or a dehydroxylated aluminosilicate. It is preferably obtained by dehydration of a kaolin or of a kaolinite. This dehydration is conventionally obtained by calcination. The liquid geopolymer composition may comprise from 5 to 50% by weight approximately of aluminosilicate, and preferably from 10 to 35% by weight approximately of aluminosilicate, relative to the total weight of the liquid geopolymer composition.
La composition géopolymère liquide peut comprendre en outre un deuxième aluminosilicate différent du premier aluminosilicate. The liquid geopolymer composition may further comprise a second aluminosilicate different from the first aluminosilicate.
De préférence, la composition géopolymère liquide comprend deux kaolins calcinés ayant des températures de calcination différentes. Preferably, the liquid geopolymer composition comprises two calcined kaolins having different calcination temperatures.
Selon une forme de réalisation particulièrement préférée de l'invention, la composition géopolymère liquide comprend un premier métakaolin choisi parmi les kaolins calcinés à une température Tci d'au moins 650°C environ, et un deuxième métakaolin choisi parmi les kaolins calcinés à une température TC2 telle que TC2 - Tci > 100°C environ, au moins un premier silicate alcalin, de l'eau, et éventuellement une base alcaline. La composition géopolymère liquide peut alors présenter des propriétés mécaniques améliorées, notamment en termes de flexibilité et de durabilité, tout en garantissant de bonnes propriétés de réaction et de résistance au feu. According to a particularly preferred embodiment of the invention, the liquid geopolymer composition comprises a first metakaolin chosen from kaolins calcined at a temperature T ci of at least 650 ° C approximately, and a second metakaolin chosen from kaolins calcined at a temperature temperature T C 2 such that T C 2 - T ci > 100 ° C approximately, at least a first alkali metal silicate, water, and optionally an alkaline base. The liquid geopolymer composition can then exhibit improved mechanical properties, in particular in terms of flexibility and durability, while ensuring good reaction and fire resistance properties.
Le deuxième métakaolin étant choisi parmi les kaolins calcinés à une température TC2 telle que TC2 - Tci > 100°C environ, il est différent du premier métakaolin tel que défini dans l'invention. The second metakaolin being chosen from kaolins calcined at a temperature T C 2 such as T C 2 - T ci > 100 ° C approximately, it is different from the first metakaolin as defined in the invention.
Selon une forme de réalisation de l'invention, le premier métakaolin est un kaolin calciné à une température Tci d'au moins 700°C environ, et de préférence d'au moins 725°C environ. According to one embodiment of the invention, the first metakaolin is a kaolin calcined at a temperature T ci of at least approximately 700 ° C, and preferably of at least 725 ° C approximately.
Selon une forme de réalisation préférée de l'invention, le premier métakaolin est un kaolin calciné à une température Tci d'au plus 875°C environ, et de préférence d'au plus 825°C environ. According to a preferred embodiment of the invention, the first metakaolin is a kaolin calcined at a temperature T ci of at most 875 ° C approximately, and preferably at most 825 ° C approximately.
Le premier métakaolin peut comprendre au moins 20% en mole environ, et de préférence au moins 30% en mole environ d'oxyde d'aluminium (AI2O3), par rapport au nombre de moles total du premier métakaolin. The first metakaolin can comprise at least 20 mol% approximately, and preferably at least 30 mol% approximately, of aluminum oxide (Al2O3), relative to the total number of moles of the first metakaolin.
Le premier métakaolin peut comprendre au plus 60% en mole environ, et de préférence au plus 50% en mole environ d'oxyde d'aluminium (AI2O3), par rapport au nombre de moles total du premier métakaolin. Le premier métakaolin peut comprendre au moins 35% en mole environ, et de préférence au moins 45% en mole environ d'oxyde de silicium (S1O2), par rapport au nombre de moles total du premier métakaolin. The first metakaolin may comprise at most 60 mol% approximately, and preferably at most 50 mol% approximately, of aluminum oxide (Al2O3), relative to the total number of moles of the first metakaolin. The first metakaolin may comprise at least 35 mol% approximately, and preferably at least 45 mol% approximately, of silicon oxide (S1O2), relative to the total number of moles of the first metakaolin.
Le premier métakaolin peut comprendre au plus 75% en mole environ, et de préférence au plus 65% en mole environ d'oxyde de silicium (S1O2), par rapport au nombre de moles total du premier métakaolin. The first metakaolin may comprise at most 75 mol% approximately, and preferably at most 65 mol% approximately, of silicon oxide (S1O2), relative to the total number of moles of the first metakaolin.
À titre d'exemples de premier métakaolin, on peut citer les métakaolins vendus par la société Imérys, notamment celui commercialisé sous la référence PoleStar® 450. As examples of the first metakaolin, mention may be made of the metakaolins sold by the company Imérys, in particular that marketed under the reference PoleStar ® 450.
Le premier métakaolin peut être choisi parmi les kaolins calcinés à Tci telle que définie dans l'invention, pendant au moins 1 min environ, de préférence pendant au moins 10 min environ, de façon particulièrement préférée pendant une durée allant d'environ 30 min à 8h, et de façon plus particulièrement préférée pendant une durée allant d'environ 2h à 6h. The first metakaolin can be chosen from kaolins calcined at T ci as defined in the invention, for at least approximately 1 min, preferably for at least approximately 10 min, particularly preferably for a period ranging from approximately 30 min. at 8 h, and more particularly preferably for a period ranging from approximately 2 h to 6 h.
Le deuxième métakaolin est choisi de préférence parmi les kaolins calcinés à une température TC2 telle que TC2 - Tci > 150°C environ, de façon particulièrement préférée telle que TC2 - Tci > 200°C environ, et de façon plus particulièrement préférée telle que TC2 - Tci > 250°C environ. The second metakaolin is preferably chosen from kaolins calcined at a temperature T C 2 such that T C 2 - T ci > 150 ° C approximately, particularly preferably such that T C 2 - T ci > 200 ° C approximately, and more particularly preferably such that T C 2 - T ci > 250 ° C approximately.
Selon une forme de réalisation de l'invention, le deuxième métakaolin est un kaolin calciné à une température TC2 d'au moins 800°C environ, de préférence d'au moins 850°C environ, et de façon particulièrement préférée d'au moins 900°C environ. According to one embodiment of the invention, the second metakaolin is a kaolin calcined at a temperature T C 2 of at least 800 ° C approximately, preferably at least 850 ° C approximately, and particularly preferably of at least about 900 ° C.
Selon une forme de réalisation préférée de l'invention, le deuxième métakaolin est un kaolin calciné à une température TC2 d'au plus 1200°C environ, et de préférence d'au plus 1150°C environ. According to a preferred embodiment of the invention, the second metakaolin is a kaolin calcined at a temperature T C 2 of at most 1200 ° C approximately, and preferably at most 1150 ° C approximately.
Le deuxième métakaolin peut comprendre au moins 20% en mole environ, et de préférence au moins 30% en mole environ d'oxyde d'aluminium (AI2O3), par rapport au nombre de moles total du deuxième métakaolin. The second metakaolin can comprise at least 20 mol% approximately, and preferably at least 30 mol% approximately, of aluminum oxide (Al 2 O 3 ), relative to the total number of moles of the second metakaolin.
Le deuxième métakaolin peut comprendre au plus 60% en mole environ, et de préférence au plus 50% en mole environ d'oxyde d'aluminium (AI2O3), par rapport au nombre de moles total du deuxième métakaolin. Le deuxième métakaolin peut comprendre au moins 35% en mole environ, et de préférence au moins 45% en mole environ d'oxyde de silicium (S1O2), par rapport au nombre de moles total du deuxième métakaolin. The second metakaolin can comprise at most 60 mol% approximately, and preferably at most 50 mol% approximately, of aluminum oxide (Al2O3), relative to the total number of moles of the second metakaolin. The second metakaolin can comprise at least 35 mol% approximately, and preferably at least 45 mol% approximately of silicon oxide (S1O2), relative to the total number of moles of the second metakaolin.
Le deuxième métakaolin peut comprendre au plus 75% en mole environ, et de préférence au plus 65% en mole environ d'oxyde de silicium (S1O2), par rapport au nombre de moles total du deuxième métakaolin. The second metakaolin can comprise at most 75 mol% approximately, and preferably at most 65 mol% approximately of silicon oxide (S1O2), relative to the total number of moles of the second metakaolin.
À titre d'exemples de deuxième métakaolin, on peut citer les métakaolins vendus par la société Imérys, notamment celui commercialisé sous la référence PoleStar® 200R. Examples of second metakaolin include metakaolins sold by Imérys society, especially that marketed under the reference PoleStar ® 200R.
Le deuxième métakaolin peut être choisi parmi les kaolins calcinés à TC2 telle que définie dans l'invention, pendant au moins 1 min environ, de préférence pendant au moins 5 min environ, de façon particulièrement préférée pendant une durée allant d'environ 10 min à 2h, et de façon plus particulièrement préférée pendant une durée allant d'environ 15 min à lh. The second metakaolin can be chosen from kaolins calcined at T C 2 as defined in the invention, for at least approximately 1 min, preferably for at least approximately 5 min, particularly preferably for a period ranging from approximately 10 min to 2 h, and more particularly preferably for a period ranging from approximately 15 min to 1 h.
Le rapport massique [premier métakaolin/deuxième métakaolin] dans la composition géopolymère liquide va de préférence de 0,1 à 2 environ, de façon particulièrement préférée de 0,5 à 1,0 environ, et de façon plus particulièrement préférée est d'environ 1. The mass ratio [first metakaolin / second metakaolin] in the liquid geopolymer composition is preferably from 0.1 to 2 approximately, particularly preferably from 0.5 to 1.0 approximately, and more particularly preferably is approximately 1.
La composition géopolymère liquide peut comprendre de 5 à 50% en poids environ, et de préférence de 10 à 35% en poids environ de premier et deuxième métakaolins, par rapport au poids total de la composition géopolymère liquide. The liquid geopolymer composition can comprise from 5 to 50% by weight approximately, and preferably from 10 to 35% by weight approximately of first and second metakaolins, relative to the total weight of the liquid geopolymer composition.
Les premier et deuxième métakaolins peuvent être analysés par analyse thermique différentielle (ATD) [absence ou présence d'un point ou pic de cristallisation], résonance magnétique nucléaire (RMN) [spectre RMN27 Al], et/ou diffraction aux rayons X (DRX). The first and second metakaolins can be analyzed by differential thermal analysis (DTA) [absence or presence of a crystallization point or peak], nuclear magnetic resonance (NMR) [ 27 Al NMR spectrum], and / or X-ray diffraction ( DRX).
Le premier métakaolin présente de préférence un pic de cristallisation par analyse thermique différentielle, de façon particulièrement préférée à une température allant de 900 à 1060°C, et de façon plus particulièrement préférée à une température allant de 950 à 1010°C. The first metakaolin preferably exhibits a crystallization peak by differential thermal analysis, particularly preferably at a temperature ranging from 900 to 1060 ° C, and more particularly preferably at a temperature ranging from 950 to 1010 ° C.
Le deuxième métakaolin comprend de préférence de la mullite. Le premier silicate alcalin The second metakaolin preferably comprises mullite. The first alkali silicate
Le premier silicate alcalin peut être choisi parmi les silicates de sodium, les silicates de potassium, et l'un de leurs mélanges. The first alkali silicate can be chosen from sodium silicates, potassium silicates, and one of their mixtures.
Les silicates alcalins commercialisés par la société Silmaco ou par la société PQ corporation sont préférés. Le premier silicate alcalin est de préférence un silicate de sodium. The alkali metal silicates marketed by the company Silmaco or by the company PQ corporation are preferred. The first alkali silicate is preferably sodium silicate.
Le premier silicate alcalin peut avoir un rapport molaire S1O2/M2O allant de 1,1 à 35 environ, de préférence de 1,3 à 10 environ, et de façon particulièrement préférée de 1,4 à 5 environ, avec M étant un atome de sodium ou de potassium, et de préférence un atome de sodium. The first alkali silicate may have an S1O2 / M2O molar ratio ranging from about 1.1 to about 35, preferably from about 1.3 to 10, and particularly preferably from about 1.4 to 5, with M being an atom of sodium or potassium, and preferably a sodium atom.
La composition géopolymère liquide peut comprendre de 5 à 60% en poids environ, et de préférence de 10 à 50% en poids environ de premier silicate alcalin, par rapport au poids total de la composition géopolymère liquide. The liquid geopolymer composition can comprise from 5 to 60% by weight approximately, and preferably from 10 to 50% by weight approximately of first alkali silicate, relative to the total weight of the liquid geopolymer composition.
Le deuxième silicate alcalin The second alkali silicate
La composition géopolymère liquide peut comprendre en outre un deuxième silicate alcalin différent du premier silicate alcalin. The liquid geopolymer composition may further comprise a second alkali silicate different from the first alkali silicate.
Le deuxième silicate alcalin peut être choisi parmi les silicates de sodium, les silicates de potassium, et l'un de leurs mélanges. Les silicates alcalins commercialisés par la société Silmaco ou par la société PQ Corporation sont préférés. Le deuxième silicate alcalin est de préférence un silicate de sodium. The second alkali silicate can be chosen from sodium silicates, potassium silicates, and one of their mixtures. The alkali metal silicates marketed by the company Silmaco or by the company PQ Corporation are preferred. The second alkali silicate is preferably sodium silicate.
Les premier et deuxième silicates alcalins peuvent avoir respectivement des rapports molaires SÎ02/M20 et SiC /M^O tels que M et M', identiques, sont choisis parmi un atome de sodium et un atome de potassium, et de préférence un atome de sodium, et lesdits rapports ont des valeurs différentes, de préférence des valeurs telles que leur différence est d'au moins 0,3, de façon particulièrement préférée telles que leur différence est d'au moins 0,5, et de façon plus particulièrement préférée telles que leur différence est d'au moins 1,0. The first and second alkali silicates can have respectively SÎ0 2 / M 2 0 and SiC / M 2 O molar ratios such as M and M ', which are identical, are chosen from a sodium atom and a potassium atom, and preferably a sodium atom, and said ratios have different values, preferably values such that their difference is at least 0.3, particularly preferably such that their difference is at least 0.5, and more particularly preferred such that their difference is at least 1.0.
Selon une forme de réalisation de l'invention, la composition géopolymère liquide comprend : According to one embodiment of the invention, the liquid geopolymer composition comprises:
- un premier silicate alcalin ayant un rapport molaire SÎ02/M20 allant de 1,5 à 2,6 environ, et - un deuxième silicate alcalin ayant un rapport molaire Si02/M'20 supérieur à 2,6, de préférence allant de 2,8 à 4,5 environ, et de façon particulièrement préférée allant de 3,0 à 4,0 environ, étant entendu que M' est identique à M. - a first alkali silicate having a molar ratio SÎO2 / M20 ranging from 1.5 to 2.6 approximately, and - a second alkali silicate having an SiO 2 / M'20 molar ratio greater than 2.6, preferably ranging from 2.8 to 4.5 approximately, and particularly preferably ranging from 3.0 to 4.0 approximately, being understood that M 'is identical to M.
La composition géopolymère liquide peut comprendre de 10 à 60% en poids environ, et de préférence de 20 à 50% en poids environ de premier et deuxième silicates alcalins, par rapport au poids total de la composition géopolymère liquide. The liquid geopolymer composition can comprise from 10 to 60% by weight approximately, and preferably from 20 to 50% by weight approximately of first and second alkali silicates, relative to the total weight of the liquid geopolymer composition.
Le rapport massique [premier silicate alcalin/deuxième silicate alcalin] dans la composition géopolymère liquide va de préférence de 0,5 à 2,5, et de façon particulièrement préférée de 0,8 à 2,0. The mass ratio [first alkali silicate / second alkali silicate] in the liquid geopolymer composition preferably ranges from 0.5 to 2.5, and particularly preferably from 0.8 to 2.0.
La base alcaline Alkaline base
La base alcaline peut être de l'hydroxyde de sodium, ou de l'hydroxyde de potassium, et de préférence de l'hydroxyde de sodium. The alkaline base can be sodium hydroxide, or potassium hydroxide, and preferably sodium hydroxide.
La composition géopolymère liquide peut être exempte de base alcaline. Cela permet ainsi d'améliorer la manipulation de la composition géopolymère liquide, en particulier lors de la préparation d'un câble. The liquid geopolymer composition may be free from an alkaline base. This thus makes it possible to improve the handling of the liquid geopolymer composition, in particular during the preparation of a cable.
Le rapport massique matières solides/eau dans ladite composition géopolymère liquide détermine la cinétique de solidification lors de l'étape ii). The solid matter / water mass ratio in said liquid geopolymer composition determines the solidification kinetics during step ii).
La composition géopolymère liquide peut comprendre de 35% à 80% en poids environ, et de façon particulièrement préférée de 40% à 70% en poids environ, de matières solides (silicate alcalin(s), aluminosilicate(s) et base alcaline), par rapport au poids total de ladite composition géopolymère liquide. The liquid geopolymer composition may comprise from 35% to 80% by weight approximately, and more preferably from 40% to 70% by weight approximately, of solid materials (alkali silicate (s), aluminosilicate (s) and alkaline base), relative to the total weight of said liquid geopolymer composition.
La composition géopolymère liquide peut comprendre en outre un ou plusieurs additifs choisis parmi : The liquid geopolymer composition may further comprise one or more additives chosen from:
- un colorant, - a dye,
- des fibres minérales, notamment choisies parmi les fibres d'alumine ou de basalte, - mineral fibers, in particular chosen from alumina or basalt fibers,
- un composé accélérant la prise en masse, notamment choisi parmi le sulfate d'aluminium, les aluns (e.g. sulfate double d'aluminium et de potassium), le chlorure de calcium, le sulfate de calcium, le sulfate de calcium hydraté, l'aluminate de sodium, le carbonate de sodium, le chlorure de sodium, le silicate de sodium, le sulfate de sodium, le chlorure de fer (III), et les lignosulfonates de sodium, - a compound accelerating the setting in mass, in particular chosen from aluminum sulphate, alums (eg double sulphate of aluminum and potassium), calcium chloride, calcium sulphate, hydrated calcium sulphate, sodium aluminate, sodium carbonate, sodium chloride, sodium silicate, sodium sulfate, iron (III) chloride, and sodium lignosulfonates,
- un agent retardant la prise en masse, notamment choisi parmi l'ammonium, les métaux alcalins, les métaux alcalino-terreux, le borax, les lignosulfonates et en particulier les sels de métaux de lignosulfonates de calcium, les lignines sulfoalkylées telles que par exemple la lignine sulfométhylée, les acides hydroxycarboxyliques, les copolymères de sels d'acide 2-acrylamido-2- méthylpropane sulfonique et d'acide acrylique ou d'acide maléique, et les sels saturés, - an agent delaying setting in mass, in particular chosen from ammonium, alkali metals, alkaline earth metals, borax, lignosulphonates and in particular metal salts of calcium lignosulphonates, sulphoalkylated lignins such as, for example, sulfomethylated lignin, hydroxycarboxylic acids, copolymers of salts of 2-acrylamido-2-methylpropane sulfonic acid and acrylic acid or maleic acid, and saturated salts,
- une charge inerte, notamment choisi parmi le talc, les micas, les argiles déshydratées, et le carbonate de calcium, - an inert filler, in particular chosen from talc, micas, dehydrated clays, and calcium carbonate,
- un matériau carboné expansé tel qu'un graphite expansé. - an expanded carbon material such as expanded graphite.
Le colorant est de préférence un colorant liquide à température ambiante (i.e. à 18-25°C). The dye is preferably a liquid dye at room temperature (i.e. at 18-25 ° C).
La composition géopolymère liquide peut comprendre de 0,01 à 15% en poids environ d'additif(s), de préférence de 0,1 à 8% en poids environ d'additif(s), et de façon particulièrement préférée de 0,5 à 5% en poids environ d'additif(s), par rapport au poids total de la composition géopolymère liquide. The liquid geopolymer composition may comprise from 0.01 to 15% by weight approximately of additive (s), preferably from 0.1 to 8% by weight approximately of additive (s), and particularly preferably 0, 5 to 5% by weight approximately of additive (s), relative to the total weight of the liquid geopolymer composition.
Le matériau fibreux non tissé The non-woven fibrous material
Dans l'étape i), le matériau fibreux non tissé se présente préférentiellement sous la forme d'un ruban ou d'une bande. In step i), the nonwoven fibrous material is preferably in the form of a ribbon or a strip.
Le matériau fibreux non tissé a de préférence une structure souple et flexible. The fibrous nonwoven material preferably has a soft and flexible structure.
Le matériau fibreux non tissé peut être choisi parmi les matériaux cellulosiques, les matériaux à base de polymères organiques synthétiques, les fibres de verre, et un de leurs mélanges, et de préférence parmi les matériaux à base de polymères organiques synthétiques. The nonwoven fibrous material can be chosen from cellulosic materials, materials based on synthetic organic polymers, glass fibers, and a mixture thereof, and preferably from materials based on synthetic organic polymers.
Les matériaux cellulosiques peuvent être choisis parmi le papier, en particulier le papier buvard ; les matériaux non tissés fabriqués à partir de cellulose fonctionnalisée ou non fonctionnalisée ; les matrices à structure alvéolaire et/ou fibreuse fabriquées à partir de fibres naturelles d'acétate de cellulose. The cellulosic materials can be chosen from paper, in particular blotting paper; non-woven materials made from functionalized or non-functionalized cellulose; structure matrices alveolar and / or fibrous made from natural fibers of cellulose acetate.
Les matériaux à base de polymères organiques synthétiques peuvent être choisis parmi les matériaux polymères à matrice poreuse et/ou fibreuse de polyoléfine(s), en particulier ceux choisis parmi les homo- et copolymères de propylène, les homo- et copolymères d'éthylène, les polyéthylènes haute densité (HDPE), les polyamides aromatiques (aramides), les polyesters, et un de leurs mélanges. The materials based on synthetic organic polymers can be chosen from polymer materials with a porous and / or fibrous polyolefin (s) matrix, in particular those chosen from propylene homopolymers and copolymers, ethylene homopolymers and copolymers, high density polyethylenes (HDPE), aromatic polyamides (aramids), polyesters, and a mixture thereof.
Selon une forme de réalisation préférée de l'invention, le matériau fibreux non tissé est un polyéthylène téréphtalate (PET). According to a preferred embodiment of the invention, the nonwoven fibrous material is polyethylene terephthalate (PET).
Le matériau fibreux non tissé présente de préférence un grammage allant de 50 à 120 g/cm2 environ. Cela permet ainsi d'obtenir une couche composite suffisamment flexible pour pouvoir être manipulée facilement, et suffisamment robuste pour obtenir une bonne protection au feu. The nonwoven fibrous material preferably has a basis weight ranging from 50 to 120 g / cm 2 approximately. This thus makes it possible to obtain a composite layer which is sufficiently flexible to be able to be handled easily, and sufficiently robust to obtain good fire protection.
L'étape i) peut être effectuée manuellement ou de façon automatisée, et de préférence de façon automatisée. Step i) can be carried out manually or automatically, and preferably automatically.
Lorsqu'elle est automatisée, l'étape i) est effectuée à une vitesse allant de 20 à 280 m/min environ, et de préférence allant de 50 à 150 m/min environ. When it is automated, step i) is carried out at a speed ranging from 20 to 280 m / min approximately, and preferably ranging from 50 to 150 m / min approximately.
L'étape d'imprégnation i) peut être effectuée sur le matériau fibreux non tissé seul (dénommée ci-après première variante), ou sur un ensemble matériau fibreux non tissé/câble comprenant au moins un élément électriquement conducteur allongé (dénommé ci-après deuxième variante). The impregnation step i) can be carried out on the nonwoven fibrous material alone (hereinafter referred to as the first variant), or on a nonwoven fibrous material / cable assembly comprising at least one elongate electrically conductive element (hereinafter referred to as second variant).
Première variante First variant
Selon la première variante, l'étape i) est une étape i-vl) et elle est de préférence effectuée par enduction imprégnation, et de façon particulièrement préférée par enduction pré-contrôlée. According to the first variant, step i) is step i-vl) and it is preferably carried out by impregnation coating, and particularly preferably by pre-controlled coating.
L'étape i-vl) peut par exemple être effectuée à l'aide d'un dispositif d'enduction tel qu'une filière d'enduction. Ce dispositif est particulièrement approprié pour imprégner un matériau fibreux non tissé seul, i.e. lorsqu'il n'est pas encore appliqué autour du câble. Step i-vl) can for example be carried out using a coating device such as a coating die. This device is particularly suitable for impregnating a nonwoven fibrous material alone, i.e. when it is not yet applied around the cable.
L'étape i-vl) est plus particulièrement mise en oeuvre en faisant passer le matériau fibreux non tissé dans un dispositif d'enduction tel qu'une filière d'enduction, ledit dispositif étant alimenté avec la composition géopolymère liquide, notamment à l'aide de moyens tels qu'une pompe. Cela permet ainsi de distribuer directement la quantité voulue de la composition géopolymère liquide de façon homogène sur toute la largeur désirée dudit matériau fibreux non tissé. Step i-vl) is more particularly carried out by passing the nonwoven fibrous material through a coating device such as a die. coating, said device being supplied with the liquid geopolymer composition, in particular using means such as a pump. This thus makes it possible to directly distribute the desired amount of the liquid geopolymer composition homogeneously over the entire desired width of said nonwoven fibrous material.
L'étape i-vl) peut en particulier être une enduction connue selon l'anglicisme « tensioned web die coating ». Step i-vl) can in particular be a coating known according to the anglicism “tensioned web die coating”.
Dans un mode de réalisation préféré de l'invention, l'étape i-vl) d'imprégnation est réalisée à une température allant de 15°C à 90°C environ, et de façon particulièrement préférée de 20°C à 40°C environ. In a preferred embodiment of the invention, step i-vl) of impregnation is carried out at a temperature ranging from 15 ° C to 90 ° C approximately, and particularly preferably from 20 ° C to 40 ° C. about.
Selon cette première variante, le matériau fibreux non tissé peut être disposé sur un distributeur tel qu'un dérouleur ou dévidoir, et ledit matériau peut être distribué ou déroulé en continu pour mettre en oeuvre au moins l'étape i)· According to this first variant, the nonwoven fibrous material may be placed on a dispenser such as an unwinder or unwinder, and said material may be dispensed or unwound continuously to implement at least step i)
De préférence, selon la première variante de l'invention, l'étape i-vl) est mise en oeuvre en faisant passer le matériau fibreux non tissé dans un dispositif d'enduction alimenté avec la composition géopolymère liquide avec un débit D (en kg/min), le distributeur délivre le matériau fibreux non tissé à une vitesse V (en km/min), et le rapport D/V va d'environ 20 à 50 kg de composition géopolymère liquide / km de matériau fibreux non tissé, et de façon particulièrement préférée d'environ 25 à 40 kg de composition géopolymère liquide / km de matériau fibreux non tissé. La quantité de composition géopolymère liquide appliquée sur le matériau fibreux non tissée peut ainsi être facilement ajustée par une pompe. Preferably, according to the first variant of the invention, step i-vl) is carried out by passing the nonwoven fibrous material through a coating device supplied with the liquid geopolymer composition at a flow rate D (in kg / min), the distributor delivers the nonwoven fibrous material at a speed V (in km / min), and the D / V ratio ranges from about 20 to 50 kg of liquid geopolymer composition / km of nonwoven fibrous material, and particularly preferably about 25 to 40 kg of liquid geopolymer composition / km of nonwoven fibrous material. The amount of liquid geopolymer composition applied to the nonwoven fibrous material can thus be easily adjusted by a pump.
La vitesse V est de préférence identique à la vitesse de défilement du câble. The speed V is preferably identical to the running speed of the cable.
Le débit D peut aller de 0,5 kg/min à 4,5 kg/min environ. The flow rate D can range from 0.5 kg / min to 4.5 kg / min approximately.
La vitesse V peut aller de 20 m/min à 280 m/min environ, et de préférence de 50 m/min à 150 m/min environ. Deuxième variante The speed V can range from approximately 20 m / min to 280 m / min, and preferably from 50 m / min to approximately 150 m / min. Second variant
Selon la deuxième variante, l'étape i) est une étape i-v2) et elle est de préférence effectuée par trempage enduction. According to the second variant, step i) is step i-v2) and it is preferably carried out by coating soaking.
L'étape i-v2) peut par exemple être effectuée à l'aide d'un bain ou bac d'imprégnation comprenant la composition géopolymère liquide dans lequel on introduit le câble comprenant au moins un élément électriquement conducteur allongé et un matériau fibreux non tissé entourant ledit élément électriquement conducteur allongé. Step i-v2) can for example be carried out using an impregnation bath or tank comprising the liquid geopolymer composition into which is introduced the cable comprising at least one elongated electrically conductive element and a nonwoven fibrous material. surrounding said elongated electrically conductive member.
Le bain ou bac d'imprégnation est de préférence configuré pour permettre le passage du câble comprenant au moins un élément électriquement conducteur allongé et un matériau fibreux non tissé entourant ledit élément électriquement conducteur allongé, au travers dudit bain d'imprégnation. The bath or impregnation tank is preferably configured to allow passage of the cable comprising at least one elongated electrically conductive element and a nonwoven fibrous material surrounding said elongated electrically conductive element, through said impregnation bath.
La composition géopolymère liquide est alors introduite dans ledit bain d'imprégnation, pour permettre l'étape i-v2). The liquid geopolymer composition is then introduced into said impregnation bath, to allow step i-v2).
Le bain ou bac d'imprégnation est de préférence alimenté avec la composition géopolymère liquide, notamment à l'aide de moyens tels qu'une pompe. Cela permet ainsi d'alimenter en continu ledit bain ou bac en composition géopolymère liquide. The bath or impregnation tank is preferably supplied with the liquid geopolymer composition, in particular using means such as a pump. This thus makes it possible to continuously supply said bath or tank with liquid geopolymer composition.
Dans un mode de réalisation préféré de l'invention, l'étape i-v2) d'imprégnation est réalisée à une température allant de 15°C à 40°C environ, et de façon particulièrement préférée de 20°C à 30°C environ. In a preferred embodiment of the invention, the impregnation step i-v2) is carried out at a temperature ranging from 15 ° C to 40 ° C approximately, and particularly preferably from 20 ° C to 30 ° C. about.
La vitesse V est de préférence identique à la vitesse de défilement du câble. The speed V is preferably identical to the running speed of the cable.
De préférence, l'étape i-v2) est mise en oeuvre en faisant passer le câble comprenant ledit élément électriquement conducteur allongé et ledit matériau fibreux non tissé entourant ledit élément électriquement conducteur allongé dans un bain ou bac d'imprégnation alimenté avec la composition géopolymère avec un débit D (en kg/min). Le débit D peut aller de 0,5 kg/min à 4,5 kg/min environ. Preferably, step i-v2) is carried out by passing the cable comprising said elongated electrically conductive element and said nonwoven fibrous material surrounding said elongated electrically conductive element in an impregnation bath or tank supplied with the geopolymer composition. with a flow rate D (in kg / min). The flow rate D can range from 0.5 kg / min to 4.5 kg / min approximately.
La vitesse de défilement du câble dans l'étape i-v2) peut aller de 20 m/min à 280 m/min environ, et de préférence de 50 m/min à 150 m/min environ. Le matériau fibreux non tissé imprégné de la composition géopolymère liquide (première variante) ou l'ensemble câble/matériau fibreux non tissé imprégné de la composition géopolymère liquide (première variante) est alors directement utilisé dans l'étape ii) ou l'étape a) telle que définie dans l'invention. The cable running speed in step i-v2) can range from approximately 20 m / min to 280 m / min, and preferably from 50 m / min to approximately 150 m / min. The nonwoven fibrous material impregnated with the liquid geopolymer composition (first variant) or the cable / nonwoven fibrous material assembly impregnated with the liquid geopolymer composition (first variant) is then directly used in step ii) or step a ) as defined in the invention.
Etape a) d'aiout d'une composition gélifiante Step a) of adding a gelling composition
L'étape a) d'ajout d'une composition gélifiante peut être effectuée avant l'étape i) ou après l'étape i) d'imprégnation du matériau fibreux non tissé. Step a) of adding a gelling composition can be carried out before step i) or after step i) of impregnating the nonwoven fibrous material.
L'étape a) permet ainsi d'ajouter à la composition géopolymère liquide seule (i.e. avant l'étape i)) ou à la composition géopolymère liquide imprégnant le matériau fibreux non tissé (i.e. après l'étape i)) la composition gélifiante. Step a) thus makes it possible to add to the liquid geopolymer composition alone (i.e. before step i)) or to the liquid geopolymer composition impregnating the nonwoven fibrous material (i.e. after step i)) the gelling composition.
La composition gélifiante est en d'autres termes une composition précurseur d'un gel ou une composition apte à former un gel, en particulier lorsqu'elle est ajoutée à la composition géopolymère liquide. The gelling composition is in other words a precursor composition of a gel or a composition capable of forming a gel, in particular when it is added to the liquid geopolymer composition.
La composition gélifiante peut comprendre au moins un composé précurseur d'un gel choisi parmi les polymères organiques réticulables, les polysaccharides, les monomères organiques, et un de leurs mélanges. The gelling composition can comprise at least one precursor compound of a gel chosen from crosslinkable organic polymers, polysaccharides, organic monomers, and one of their mixtures.
Parmi les polysaccharides, on peut citer les amidons, les amidons modifiés, les alginates, les alginates modifiés, le chitosan, l'acide hyaluronique, les carraghénanes, les gommes polysaccharidiques telles que l'agar-agar, la gomme xanthane ou la gomme gellane, les pectines, la cellulose, les dérivés de la cellulose, les dextranes modifiés, et l'acide hyaluronique. Among the polysaccharides, mention may be made of starches, modified starches, alginates, modified alginates, chitosan, hyaluronic acid, carrageenans, polysaccharide gums such as agar-agar, xanthan gum or gellan gum , pectins, cellulose, cellulose derivatives, modified dextrans, and hyaluronic acid.
De préférence, le polysaccharide utilisé est sous la forme d'une poudre.Preferably, the polysaccharide used is in the form of a powder.
Parmi les polymères organiques réticulables on peut citer les polyorganosiloxanes, et les poly(méth)acrylates. Among the crosslinkable organic polymers, mention may be made of polyorganosiloxanes and poly (meth) acrylates.
Parmi les monomères organiques on peut citer les acrylates, les méthacrylates, et les acrylamides. Among the organic monomers, mention may be made of acrylates, methacrylates and acrylamides.
La composition gélifiante peut comprendre en outre un agent de réticulation et/ou un catalyseur de réticulation et/ou un initiateur, notamment lorsque le composé précurseur d'un gel est choisi parmi les polymères organiques réticulables, et les monomères organiques. La composition gélifiante peut comprendre en outre un ou plusieurs agents de viscosité (i.e. qui augmente la viscosité de ladite composition), tels que par exemple du chlorure de calcium, du carbonate de calcium, ou un de leur mélange, notamment lorsque le composé précurseur d'un gel est choisi parmi les polysaccharides, et en particulier les alginates. The gelling composition may further comprise a crosslinking agent and / or a crosslinking catalyst and / or an initiator, in particular when the precursor compound of a gel is chosen from crosslinkable organic polymers and organic monomers. The gelling composition may further comprise one or more viscosity agents (ie which increases the viscosity of said composition), such as, for example, calcium chloride, calcium carbonate, or a mixture thereof, in particular when the precursor compound d a gel is chosen from polysaccharides, and in particular alginates.
L'agent de viscosité est préférentiellement soluble dans la composition gélifiante à une température allant de 15 à 40°C environ. The viscosity agent is preferably soluble in the gelling composition at a temperature ranging from 15 to 40 ° C approximately.
Le composé précurseur d'un gel est de préférence choisi parmi les polysaccharides, et de façon particulièrement préférée parmi les alginates et les amidons, et de façon plus particulièrement préférée sous la forme d'une poudre. The precursor compound of a gel is preferably chosen from polysaccharides, and particularly preferably from alginates and starches, and more particularly preferably in the form of a powder.
L'étape a) est de préférence effectuée après l'étape i). Step a) is preferably carried out after step i).
Selon une forme de réalisation préférée de l'invention, l'ajout de la composition gélifiante a) peut être effectué par pulvérisation d'une poudre de la composition gélifiante sur la composition géopolymère liquide ; ou par mélange d'une composition gélifiante liquide avec la composition géopolymère liquide. According to a preferred embodiment of the invention, the addition of the gelling composition a) can be carried out by spraying a powder of the gelling composition onto the liquid geopolymer composition; or by mixing a liquid gelling composition with the liquid geopolymer composition.
La pulvérisation d'une poudre de la composition gélifiante sur la composition géopolymère liquide est préférée. Spraying a powder of the gelling composition onto the liquid geopolymer composition is preferred.
Lorsque la pulvérisation a) est utilisée après l'étape i), le matériau non tissé imprégné de la composition géopolymère peut par exemple passer dans une cellule de pulvérisation comprenant une chambre tubulaire et des tubulures permettant la pulvérisation de la composition gélifiante sur le matériau fibreux non tissé imprégné [étapes a) et ii)]. When the spraying a) is used after step i), the nonwoven material impregnated with the geopolymer composition can for example pass into a spray cell comprising a tubular chamber and nozzles allowing the spraying of the gelling composition on the fibrous material. impregnated nonwoven [steps a) and ii)].
La cellule de pulvérisation peut être connectée à un dispositif de resserrement, notamment pour permettre le confinement de l'ensemble gel/matériau non tissé autour de l'élément électriquement conducteur allongé lorsque la deuxième variante est utilisée pour l'étape iii) décrite ci-après. The spray cell can be connected to a tightening device, in particular to allow the confinement of the gel / nonwoven material assembly around the elongated electrically conductive element when the second variant is used for step iii) described below. after.
Etape ii) de formation d'un gel encapsulant le matériau fibreux non tisséStep ii) forming a gel encapsulating the nonwoven fibrous material
L'étape ii) permet d'amener la composition géopolymère liquide d'un état liquide à un état de gel lié à la présence d'une composition gélifiante. Step ii) makes it possible to bring the liquid geopolymer composition from a liquid state to a gel state linked to the presence of a gelling composition.
L'étape ii) peut être concomitante avec l'étape a). En d'autres termes, l'ajout de la composition gélifiante à la composition géopolymère liquide permet de former directement un gel encapsulant le matériau non tissé. L'étape ii) peut être réalisée après l'étape a). De préférence, dans ce mode de réalisation l'étape ii) est mise en oeuvre en présence d'un stimulus externe, tel que la température ou la présence de rayons UV, par exemple pour déclencher une réticulation. Step ii) can be concomitant with step a). In other words, the addition of the gelling composition to the liquid geopolymer composition makes it possible to directly form a gel encapsulating the nonwoven material. Step ii) can be carried out after step a). Preferably, in this embodiment, step ii) is carried out in the presence of an external stimulus, such as temperature or the presence of UV rays, for example to trigger crosslinking.
Grâce aux étapes a) et ii), un gel encapsulant le matériau fibreux non tissé se forme, ledit gel comprenant un matériau géopolymère. Cela permet ainsi de pomper une partie de l'eau en excès et/ou de sécher au moins en surface l'ensemble matériau fibreux non tissé/matériau polymère, et ainsi d'obtenir une couche composite dont les propriétés mécaniques sont conservées dans le temps. Thanks to steps a) and ii), a gel encapsulating the nonwoven fibrous material is formed, said gel comprising a geopolymer material. This thus makes it possible to pump part of the excess water and / or to dry at least on the surface the whole non-woven fibrous material / polymer material, and thus to obtain a composite layer whose mechanical properties are retained over time. .
Grâce à la présence de cette composition gélifiante, un réseau chimique ou physique, volumique ou surfacique est obtenu au cours de l'étape ii) qui maintient le matériau fibreux non tissé en place et/ou l'encapsule et/ou joue le rôle de support ; tout en protégeant la couche composite obtenue d'une perte d'eau dans le temps. Thanks to the presence of this gelling composition, a chemical or physical, volume or surface network is obtained during step ii) which keeps the nonwoven fibrous material in place and / or encapsulates it and / or plays the role of support; while protecting the composite layer obtained from water loss over time.
Le procédé ne comprend pas de préférence d'étape de séchage, notamment de par la présence de l'étape ii). En effet, le gel peut permettre d'assurer une gélification de surface, apportant ainsi à la fin de l'étape ii) une texture sèche au toucher après fixation de l'eau. The method preferably does not include a drying step, in particular due to the presence of step ii). In fact, the gel can make it possible to ensure surface gelation, thus providing at the end of step ii) a texture that is dry to the touch after fixing of the water.
Etape inj de préparation de la composition aéopolvmère liquide Inj step of preparation of the liquid aeropolymer composition
Le procédé peut comprendre en outre avant l'étape i), une étape i0) de préparation de la composition géopolymère liquide. The method may further comprise, before step i), a step i 0 ) of preparing the liquid geopolymer composition.
L'étape io) est généralement effectuée à un pH élevé, notamment variant de 10 à 13. Step io) is generally carried out at a high pH, in particular varying from 10 to 13.
L'étape io) comprend de préférence les sous-étapes suivantes :Step io) preferably comprises the following sub-steps:
101) la préparation d'une solution aqueuse du premier silicate alcalin, et1 01 ) the preparation of an aqueous solution of the first alkali silicate, and
102) le mélange du premier aluminosilicate sous forme de poudre avec la solution aqueuse de silicate alcalin préparée à la sous-étape iOl) précédente. 102) mixing the first aluminosilicate in powder form with the aqueous solution of alkali metal silicate prepared in the preceding sub-step iO1).
La solution aqueuse du premier silicate alcalin peut être préparée en mélangeant du dioxyde de silicium S1O2 ou un silicate alcalin avec une base MOH dans laquelle M est K ou Na. The aqueous solution of the first alkali silicate can be prepared by mixing silicon dioxide S1O2 or an alkali silicate with an MOH base in which M is K or Na.
Le dioxyde de silicium S1O2 peut être choisi parmi la fumée de silice (i.e. silice pyrogénée), le quartz, et leurs mélanges. La sous-étape ioi) peut être effectuée en dissolvant la base alcaline dans de l'eau, entraînant un dégagement de chaleur (réaction exothermique), puis en ajoutant la silice (ou le silicate alcalin). La chaleur dégagée accélère alors la dissolution de la silice (ou du silicate alcalin) lors de la sous-étape ioi), et du premier aluminosilicate lors de la sous-étape 102). The silicon dioxide S1O2 can be chosen from silica fume (ie fumed silica), quartz, and mixtures thereof. Sub-step ioi) can be carried out by dissolving the alkaline base in water, causing the release of heat (exothermic reaction), then adding the silica (or the alkali silicate). The heat released then accelerates the dissolution of the silica (or of the alkali silicate) during the sub-step ioi), and of the first aluminosilicate during the sub-step 102).
Lorsque le deuxième aluminosilicate et/ou le deuxième silicate alcalin tel(s) que défini(s) dans l'invention existe(nt), l'étape io) de préparation de la composition géopolymère liquide peut comprendre le mélange dudit premier aluminosilicate (de préférence sous forme de poudre) et éventuellement dudit deuxième aluminosilicate (de préférence sous forme de poudre), avec ledit premier silicate alcalin (de préférence sous forme d'une solution aqueuse), et éventuellement ledit deuxième silicate alcalin (de préférence sous forme d'une solution aqueuse). When the second aluminosilicate and / or the second alkali silicate as defined in the invention exists, step io) of preparing the liquid geopolymer composition may comprise mixing said first aluminosilicate (of preferably in powder form) and optionally said second aluminosilicate (preferably in powder form), with said first alkali silicate (preferably in the form of an aqueous solution), and optionally said second alkali silicate (preferably in the form of an aqueous solution).
L'étape io) comprend de préférence le mélange des premier et deuxième métakaolins, avec le premier silicate alcalin et éventuellement le deuxième silicate alcalin, de l'eau, et éventuellement une base alcaline. Step io) preferably comprises mixing the first and second metakaolins, with the first alkali silicate and optionally the second alkali silicate, water, and optionally an alkaline base.
Les premier et deuxième métakaolins et les premier et deuxième silicates alcalins sont tels que définis dans l'invention. The first and second metakaolins and the first and second alkali silicates are as defined in the invention.
Selon une forme de réalisation préférée, l'étape io) comprend les sous- étapes suivantes : ioa) le mélange des premier et deuxième silicates alcalins, de préférence sous forme de solutions aqueuses, notamment sous agitation, iob) éventuellement l'ajout d'une base alcaline, notamment en maintenant l'agitation, et ioc) l'ajout des premier et deuxième métakaolins, de préférence sous forme de poudres, notamment en maintenant l'agitation. According to a preferred embodiment, step io) comprises the following sub-steps: ioa) the mixture of the first and second alkali metal silicates, preferably in the form of aqueous solutions, in particular with stirring, iob) optionally the addition of an alkaline base, in particular while maintaining the agitation, and ioc) the addition of the first and second metakaolins, preferably in the form of powders, in particular while maintaining the agitation.
À l'issue de l'étape i0), ou de la sous-étape i0 ) ou i0c), on obtient préférentiellement une solution fluide et homogène. At the end of step i 0 ), or of sub-step i 0 ) or i 0c ), a fluid and homogeneous solution is preferably obtained.
À l'issue de l'étape io), la composition géopolymère peut comprendre de 35% à 80% en poids environ, et de façon particulièrement préférée de 40% à 70% en poids environ, de matières solides (silicate alcalin(s), aluminosilicate(s), et base alcaline), par rapport au poids total de ladite composition géopolymère liquide. At the end of step io), the geopolymer composition can comprise from 35% to 80% by weight approximately, and particularly preferably from 40% to 70% by weight approximately, of solid materials (alkali silicate (s) , aluminosilicate (s), and alkaline base), relative to the total weight of said liquid geopolymer composition.
Un tel rapport massique permet d'avoir une composition géopolymère liquide assez fluide pour permettre sa manipulation, et dont la cinétique de solidification est assez lente pour permettre la formation d'une couche composite de câble telle que définie ci-après. Such a mass ratio makes it possible to have a liquid geopolymer composition that is fluid enough to allow it to be handled, and the solidification kinetics of which are slow enough to allow the formation of a composite cable layer as defined below.
Le rapport massique matières solides/eau dans ladite composition géopolymère liquide peut permettre de déterminer la cinétique de solidification de ladite composition géopolymère liquide. The solid matter / water mass ratio in said liquid geopolymer composition can make it possible to determine the solidification kinetics of said liquid geopolymer composition.
L'étape io) est de préférence effectuée à température ambiante (18-25°C environ). Step io) is preferably carried out at ambient temperature (approximately 18-25 ° C.).
Etape iii) d'application du matériau fibreux non tissé autour du câbleStep iii) application of the non-woven fibrous material around the cable
Le procédé peut comprendre en outre une étape iii) d'application du matériau fibreux non tissé autour d'un câble comprenant au moins un élément électriquement conducteur allongé. The method may further comprise a step iii) of applying the nonwoven fibrous material around a cable comprising at least one elongated electrically conductive element.
L'étape iii) peut être effectuée soit après l'étape i) d'imprégnation, lorsque cette dernière met en oeuvre le matériau fibreux non tissé seul [première variante de l'invention ou étape i-vl)], soit avant l'étape i) d'imprégnation, lorsque cette dernière met en oeuvre l'ensemble câble/matériau fibreux non tissé [deuxième variante de l'invention ou étape i-v2)]. Step iii) can be carried out either after impregnation step i), when the latter uses the nonwoven fibrous material alone [first variant of the invention or step i-vl)], or before the impregnation step i), when the latter uses the cord / nonwoven fibrous material assembly [second variant of the invention or step i-v2)].
Première variante First variant
Selon la première variante de l'étape i) de l'invention (i.e. lorsque l'étape i) est une étape i-vl)), l'étape iii) est alors une étape iii-vl). According to the first variant of step i) of the invention (i.e. when step i) is a step i-vl)), step iii) is then a step iii-vl).
L'étape iii-vl) est préférentiellement effectuée après l'étape ii) telle que définie dans l'invention. Step iii-vl) is preferably carried out after step ii) as defined in the invention.
Ainsi, le matériau fibreux non tissé seul est imprégné avec la composition géopolymère liquide selon l'étape i), un gel est formé selon l'étape ii), puis l'ensemble gel/matériau fibreux non tissé est appliqué autour de l'élément électriquement conducteur allongé selon l'étape iii-vl). Thus, the nonwoven fibrous material alone is impregnated with the liquid geopolymer composition according to step i), a gel is formed according to step ii), then the gel / nonwoven fibrous material assembly is applied around the element. electrically conductive elongated according to step iii-vl).
Le matériau fibreux non tissé se présente de préférence sous la forme d'une bande ou d'un ruban. Cela permet ainsi de faciliter l'étape iii-vl). L'ensemble gel/matériau fibreux non tissé peut être appliqué soit directement autour d'un ou de plusieurs éléments conducteurs allongés, soit autour d'une couche interne dudit câble qui est elle-même autour d'un ou de plusieurs éléments conducteurs allongés. Preferably, the fibrous nonwoven material is in the form of a web or ribbon. This thus makes it possible to facilitate step iii-vl). The gel / nonwoven fibrous material assembly can be applied either directly around one or more elongated conductive elements, or around an internal layer of said cable which is itself around one or more elongated conductive elements.
Lorsque le matériau fibreux non tissé est un ruban ou une bande, l'étape iii-vl) d'application peut être effectuée par enroulement du ruban ou de la bande autour du câble. When the nonwoven fibrous material is a tape or a tape, the application step iii-vl) can be carried out by winding the tape or the tape around the cable.
L'enroulement peut être longitudinal (i.e. selon l'axe longitudinal du câble ou en d'autres termes dans le sens de la longueur du câble) ou hélicoïdal, et de préférence longitudinal. The winding can be longitudinal (i.e. along the longitudinal axis of the cable or in other words in the direction of the length of the cable) or helical, and preferably longitudinal.
L'enroulement longitudinal peut en outre être effectué avec des zones de recouvrement, la ou les zones de recouvrement représentant de 10 à 20% environ. The longitudinal winding can also be carried out with overlap zones, the overlap zone (s) representing from 10 to 20% approximately.
L'étape iii-vl) peut être effectuée manuellement ou de façon automatisée, et de préférence de façon automatisée. Step iii-vl) can be carried out manually or in an automated fashion, and preferably in an automated fashion.
L'étape iii-vl) peut être mise en oeuvre en faisant passer l'ensemble gel/matériau fibreux non tissé de l'étape ii) dans un dispositif de resserrement ou un dispositif de conformation (également par les termes « trompette » ou « conformateur de ruban »). Le câble comprenant au moins un élément électriquement conducteur allongé passe également dans le dispositif de resserrement pendant l'étape iii-vl). Ce dispositif est un dispositif mécanique qui enroule en continu l'ensemble gel/matériau fibreux non tissé autour de l'élément électriquement conducteur allongé. Cela permet ainsi de faciliter l'enroulement longitudinal de l'ensemble gel/ruban autour du câble. Step iii-vl) can be carried out by passing the gel / nonwoven fibrous material assembly of step ii) through a tightening device or a shaping device (also by the terms “trumpet” or “ tape shaper ”). The cable comprising at least one elongated electrically conductive element also passes through the tightening device during step iii-vl). This device is a mechanical device which continuously wraps the gel / nonwoven fibrous material assembly around the elongated electrically conductive element. This thus makes it possible to facilitate the longitudinal winding of the gel / ribbon assembly around the cable.
L'étape iii-vl) est de préférence effectuée à température ambiante (18- 25°C environ). Step iii-vl) is preferably carried out at ambient temperature (approximately 18-25 ° C.).
Deuxième variante Second variant
Selon la deuxième variante de l'étape i) de l'invention (i.e. lorsque l'étape i) est une étape i-v2)), l'étape iii) est alors une étape iii-v2). According to the second variant of step i) of the invention (i.e. when step i) is a step i-v2)), step iii) is then a step iii-v2).
L'étape iii-v2) est préférentiellement effectuée avant l'étape i) telle que définie dans l'invention. Ainsi, le matériau fibreux non tissé seul est d'abord appliqué autour de l'élément électriquement conducteur allongé selon l'étape iii-v2), puis l'ensemble câble/matériau non tissé est imprégné avec la composition géopolymère liquide selon l'étape i), et un gel est formé selon l'étape ii). Step iii-v2) is preferably carried out before step i) as defined in the invention. Thus, the nonwoven fibrous material alone is first applied around the elongated electrically conductive element according to step iii-v2), then the cable / nonwoven material assembly is impregnated with the liquid geopolymer composition according to step i), and a gel is formed according to step ii).
L'étape iii-v2) permet l'application du matériau non tissé autour de l'élément électriquement conducteur allongé, notamment pour former un câble comprenant au moins un élément électriquement conducteur allongé et un matériau fibreux non tissé entourant ledit élément électriquement conducteur allongé. Step iii-v2) allows the application of the nonwoven material around the elongated electrically conductive element, in particular to form a cable comprising at least one elongated electrically conductive element and a nonwoven fibrous material surrounding said elongate electrically conductive element.
Selon cette deuxième variante, le matériau fibreux non tissé peut être disposé sur un distributeur tel qu'un dérouleur ou dévidoir, et ledit matériau peut être distribué ou déroulé en continu pour mettre en oeuvre au moins l'étape iii-v2). According to this second variant, the nonwoven fibrous material may be placed on a dispenser such as an unwinder or unwinder, and said material may be dispensed or unwound continuously in order to implement at least step iii-v2).
Lors de l'étape iii-v2), le distributeur délivre le matériau fibreux non tissé à une vitesse V (en km/min). During step iii-v2), the distributor delivers the nonwoven fibrous material at a speed V (in km / min).
La vitesse V est de préférence identique à la vitesse de défilement du câble. The speed V is preferably identical to the running speed of the cable.
La vitesse V peut aller de 20 m/min à 280 m/min environ, et de préférence de 50 m/min à 150 m/min environ. The speed V can range from approximately 20 m / min to 280 m / min, and preferably from 50 m / min to approximately 150 m / min.
Le matériau fibreux non tissé se présente de préférence sous la forme d'une bande ou d'un ruban. Cela permet ainsi de faciliter l'étape iii-v2). Preferably, the fibrous nonwoven material is in the form of a web or ribbon. This thus makes it possible to facilitate step iii-v2).
Le matériau fibreux non tissé peut être appliqué soit directement autour d'un ou de plusieurs éléments conducteurs allongés, soit autour d'une couche interne dudit câble qui est elle-même autour d'un ou de plusieurs éléments conducteurs allongés. The nonwoven fibrous material can be applied either directly around one or more elongated conductive elements, or around an inner layer of said cable which is itself around one or more elongated conductive elements.
À l'issue de l'étape iii-v2), on obtient un ensemble câble/matériau fibreux non tissé, At the end of step iii-v2), a cord / nonwoven fibrous material assembly is obtained,
Lorsque le matériau fibreux non tissé est un ruban ou une bande, l'étape iii-v2) d'application peut être effectuée par enroulement du ruban autour du câble. When the nonwoven fibrous material is a tape or a tape, the application step iii-v2) can be carried out by winding the tape around the cable.
L'enroulement peut être longitudinal (i.e. selon l'axe longitudinal du câble ou en d'autres termes dans le sens de la longueur du câble) ou hélicoïdal, et de préférence longitudinal. L'enroulement longitudinal permet de diminuer le coût de production du câble. The winding can be longitudinal (ie along the longitudinal axis of the cable or in other words in the direction of the length of the cable) or helical, and preferably longitudinal. The longitudinal winding makes it possible to reduce the production cost of the cable.
L'enroulement longitudinal peut en outre être effectué avec des zones de recouvrement, la ou les zones de recouvrement représentant de 10 à 20% environ. The longitudinal winding can also be carried out with overlap zones, the overlap zone (s) representing from 10 to 20% approximately.
L'étape iii-v2) peut être effectuée manuellement ou de façon automatisée, et de préférence de façon automatisée. Step iii-v2) can be performed manually or automatically, and preferably automatically.
L'étape iii-v2) peut être mise en oeuvre en faisant passer le ruban dans un dispositif de resserrement ou un dispositif de conformation (désigné également par les termes « trompette » ou « conformateur de ruban »). Le câble comprenant au moins un élément électriquement conducteur allongé passe également dans le dispositif de resserrement pendant l'étape iii-v2). Ce dispositif est un dispositif mécanique qui enroule en continu le ruban autour de l'élément électriquement conducteur allongé. Cela permet ainsi de faciliter l'enroulement longitudinal du ruban autour du câble. Step iii-v2) can be implemented by passing the tape through a tightening device or a shaping device (also designated by the terms “trumpet” or “tape shaper”). The cable comprising at least one elongated electrically conductive element also passes through the tightening device during step iii-v2). This device is a mechanical device which continuously wraps the tape around the elongated electrically conductive element. This thus makes it possible to facilitate the longitudinal winding of the tape around the cable.
L'étape iii-v2) est de préférence effectuée à température ambiante (18- 25°C environ). Step iii-v2) is preferably carried out at ambient temperature (approximately 18-25 ° C.).
La deuxième variante est préférée. The second variant is preferred.
Etape de formation de la gaine polymère Polymer sheath formation step
Le procédé peut comprendre en outre après l'étape ii) ou l'étape iii-vl), une étape iv) d'application d'une gaine externe de protection autour de la couche composite. La gaine externe de protection peut permettre d'assurer l'intégrité mécanique du câble. The method may further comprise after step ii) or step iii-vl), a step iv) of applying a protective outer sheath around the composite layer. The outer protective sheath can ensure the mechanical integrity of the cable.
À l'issue de l'étape iv), le câble peut alors comprendre au moins un élément électriquement conducteur allongé, la couche composite entourant ledit élément électriquement conducteur allongé, et au moins une gaine externe de protection entourant ladite couche composite. At the end of step iv), the cable can then comprise at least one elongated electrically conductive element, the composite layer surrounding said elongated electrically conductive element, and at least one protective outer sheath surrounding said composite layer.
L'étape iv) est de préférence effectuée par extrusion, notamment à une température allant de 140°C à 195°C environ. Step iv) is preferably carried out by extrusion, in particular at a temperature ranging from 140 ° C to 195 ° C approximately.
L'étape iv) peut être effectuée à l'aide d'une extrudeuse. Dans ce mode de réalisation, une tête d'extrusion peut être positionnée à la sortie du dispositif de conformation tel que défini dans l'invention. Step iv) can be carried out using an extruder. In this embodiment, an extrusion head can be positioned at the outlet of the shaping device as defined in the invention.
La gaine externe de protection est de préférence la couche la plus externe du câble. The protective outer sheath is preferably the outermost layer of the cable.
La gaine externe de protection est de préférence une couche électriquement isolante. The outer protective sheath is preferably an electrically insulating layer.
La gaine externe de protection est de préférence réalisée en un matériau exempt d'halogène. Elle peut être réalisée classiquement à partir de matériaux retardant la propagation de la flamme ou résistant à la propagation de la flamme. Notamment, si ces derniers ne contiennent pas d'halogène, on parle de gainage de type HFFR (pour l'anglicisme « Halogen Free Flame Retardant »). The protective outer sheath is preferably made of a halogen-free material. It can be produced conventionally from materials retarding 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 type sheathing (for the anglicism “Halogen Free Flame Retardant”).
La gaine externe de protection peut comprendre au moins un polymère organique ou inorganique. The outer protective sheath can comprise at least one organic or inorganic polymer.
Le choix du polymère organique ou inorganique n'est pas limitatif et ceux-ci sont bien connus de l'homme du métier. The choice of organic or inorganic polymer is not limiting and these are well known to those skilled in the art.
Selon une forme de réalisation préférée de l'invention, le polymère organique ou inorganique est choisi parmi les polymères réticulés et non réticulés. According to a preferred embodiment of the invention, the organic or inorganic polymer is chosen from crosslinked and noncrosslinked polymers.
Le polymère organique ou inorganique peut être un homo- ou un co-polymère ayant des propriétés thermoplastiques et/ou élastomères. The organic or inorganic polymer can be a homo- or a co-polymer having thermoplastic and / or elastomeric properties.
Les polymères inorganiques peuvent être des polyorganosiloxanes. The inorganic polymers can be polyorganosiloxanes.
Les polymères organiques peuvent être des polyuréthanes ou des polyoléfines. The organic polymers can be polyurethanes or polyolefins.
Les polyoléfines peuvent être choisies parmi les polymères d'éthylène et de propylène. A titre d'exemple de polymères d'éthylène, on peut citer le polyéthylène linéaire basse densité (LLDPE), le polyéthylène basse densité (LDPE), le polyéthylène moyenne densité (MDPE), le polyéthylène haute densité (HDPE), les copolymères d’éthylène et d'acétate de vinyle (EVA), les copolymères d’éthylène et d’acrylate de butyle (EBA), d’acrylate de méthyle (EMA), de 2-hexyléthyl acrylate (2HEA), les copolymères d'éthylène et d'alpha- oléfines tels que par exemple les polyéthylène-octène (PEO), les copolymères d'éthylène et de propylène (EPR), les terpolymères d'éthylène et de propylène (EPT) tels que par exemple les terpolymères d'éthylène propylène diène monomère (EPDM) ou un de leurs mélanges. The polyolefins can be chosen from polymers of ethylene and propylene. By way of example of ethylene polymers, mention may be made of 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, ethylene propylene diene monomer (EPDM) terpolymers or a mixture thereof.
Le polymère de la gaine externe de protection est de préférence un polymère organique, de préférence encore un polymère d'éthylène, et de préférence encore un copolymère d’éthylène et d'acétate de vinyle, un polyéthylène linéaire basse densité, ou un de leurs mélanges. The polymer of the outer protective sheath 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 one of theirs. mixtures.
La gaine externe de protection peut comprendre en outre une charge minérale ignifugeante hydratée. Cette charge minérale ignifugeante hydratée agit principalement par voie physique en se décomposant de manière endothermique (e.g. libération d'eau), ce qui a pour conséquence d'abaisser la température de la gaine et de limiter la propagation des flammes le long du câble. On parle notamment de propriétés de retard à la flamme, bien connues sous l'anglicisme « flame retardant ». The protective outer sheath may further include a hydrated flame retardant mineral filler. This hydrated flame-retardant mineral filler acts mainly physically by decomposing endothermically (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 the anglicism “flame retardant”.
La charge minérale ignifugeante hydratée peut être un hydroxyde métallique tel que l'hydroxyde de magnésium ou le trihydroxyde d'aluminium. The hydrated flame retardant inorganic filler can be a metal hydroxide such as magnesium hydroxide or aluminum trihydroxide.
La gaine externe de protection peut comprendre en outre une charge inerte, notamment choisi parmi le talc, les micas, les argiles déshydratées et un de leurs mélanges. The outer protective sheath may further comprise an inert filler, in particular chosen from talc, micas, dehydrated clays and one of their mixtures.
La couche composite The composite layer
La couche composite est de préférence une couche électriquement isolante. The composite layer is preferably an electrically insulating layer.
Dans la présente invention, on entend par « couche électriquement isolante » une couche dont la conductivité électrique peut être d'au plus 1.109 S/m, et de préférence d'au plus 1.10 10 S/m (Siemens par mètre) (à 25°C). In the present invention, the term “electrically insulating layer” is understood to mean 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 25 ° C).
La couche composite est de préférence une couche retardante et/ou résistante au feu. The composite layer is preferably a retardant and / or fire resistant layer.
La couche composite présente de préférence une épaisseur allant de 0,2 à 3 mm environ, et de façon particulièrement préférée allant de 0,5 à 1 mm environ. The composite layer preferably has a thickness ranging from approximately 0.2 to 3 mm, and particularly preferably ranging from 0.5 to 1 mm approximately.
Lorsque l'épaisseur de la couche composite est inférieure à 0,2 mm, la protection thermique du câble obtenu selon le procédé de l'invention n'est pas suffisante. La couche composite de l'invention est de préférence une couche rubanée (i.e. sous la forme d'un ruban ou d'une bande). When the thickness of the composite layer is less than 0.2 mm, the thermal protection of the cable obtained according to the method of the invention is not sufficient. The composite layer of the invention is preferably a tape layer (ie in the form of a tape or a strip).
La couche composite présente de préférence une épaisseur sensiblement constante et constitue notamment une enveloppe de protection continue. The composite layer preferably has a substantially constant thickness and in particular constitutes a continuous protective envelope.
La couche composite peut en particulier comprendre 2 à 3 rubans superposés. The composite layer can in particular comprise 2 to 3 superimposed tapes.
La couche composite de l'invention est de préférence non poreuse. The composite layer of the invention is preferably non-porous.
La couche composite est de préférence une couche interne dudit câble.The composite layer is preferably an internal layer of said cable.
Selon l'invention, on entend par « couche interne », une couche qui ne constitue pas la couche la plus externe du câble. According to the invention, the term “internal layer” is understood to mean a layer which does not constitute the outermost layer of the cable.
La couche composite comprend de préférence au moins un matériau géopolymère, un gel (dans lequel le matériau géopolymère est dispersé), et le matériau fibreux non tissé tel que défini dans l'invention. The composite layer preferably comprises at least one geopolymeric material, a gel (in which the geopolymeric material is dispersed), and the nonwoven fibrous material as defined in the invention.
Le matériau qéopolvmère The qéopolvmère material
Dans la présente invention, le matériau géopolymère est obtenu à partir d'une composition géopolymère liquide telle que définie dans l'invention, de préférence par durcissement, géopolymérisation et/ou polycondensation de ladite composition géopolymère liquide. In the present invention, the geopolymer material is obtained from a liquid geopolymer composition as defined in the invention, preferably by curing, geopolymerization and / or polycondensation of said liquid geopolymer composition.
En particulier, la composition géopolymère liquide telle que définie dans l'invention est apte à former ledit matériau géopolymère. Les ingrédients de la composition géopolymère liquide peuvent donc subir une polycondensation pour former ledit matériau géopolymère. Le durcissement s'effectue par réaction interne du type polycondensation. Le durcissement n'est par exemple pas le résultat d’un simple séchage, comme c’est généralement le cas pour des liants à base de silicates alcalins. In particular, the liquid geopolymer composition as defined in the invention is suitable for forming said geopolymer material. The ingredients of the liquid geopolymer composition can therefore undergo polycondensation to form said geopolymer material. The hardening takes place by internal reaction of the polycondensation type. Hardening, for example, is not the result of simple drying, as is generally the case with binders based on alkali silicates.
En effet, les matériaux géopolymères résultent d’une réaction de polycondensation minérale par activation alcaline, dite géosynthèse, par opposition aux liants traditionnels hydrauliques dans lesquels le durcissement est le résultat d’une hydratation des aluminates de calcium et des silicates de calcium. Dans la présente invention, l'expression « matériau géopolymère » signifie un matériau solide comprenant du silicium (Si), de l'aluminium (Al), de l'oxygène (O) et au moins un élément choisi parmi le potassium (K), le sodium (Na), le lithium (Li), le césium (Cs) et le calcium (Ca), et de préférence choisi parmi le potassium (K), et le sodium (Na). Indeed, geopolymer materials result from a reaction of mineral polycondensation 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. In the present invention, the expression “geopolymer material” means a solid material comprising 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).
Le matériau géopolymère peut être un matériau géopolymère aluminosilicate. The geopolymer material can be an aluminosilicate geopolymer material.
Le matériau géopolymère aluminosilicate peut être choisi parmi les poly(sialates) répondant à la formule (I) Mn(-Si-0-AI-0-)n [(M)-PS] et ayant un rapport molaire Si/Al égal à 1, les poly(sialate-siloxos) répondant à la formule (II) Mn(-Si-0AI-0Si-0)n [(M)-PPS] et ayant un rapport molaire Si/Al égal à 2, les poly(sialate-disiloxos) répondant à la formule (III) Mn(-Si-0-AI-0-Si-0-Si-0)n [(M)-PSDS] et ayant un rapport molaire Si/Al égal à 3, et d'autres poly(sialates) de rapport Si/Al > 3, les poly(sialates) précités comprenant un cation alcalin M choisi parmi K, Na, Li, Cs et l'un de leurs mélanges, et n désigne le degré de polymérisation. The aluminosilicate geopolymer material can be chosen from the poly (sialates) corresponding to the formula (I) M n (-Si-0- Al-0-) n [(M) -PS] and having an equal Si / Al molar ratio to 1, the poly (sialate-siloxos) corresponding to the formula (II) M n (-Si-0AI-0Si-0) n [(M) -PPS] and having an Si / Al molar ratio equal to 2, the poly (sialate-disiloxos) corresponding to the formula (III) M n (-Si-0-Al-0-Si-0-Si-0) n [(M) -PSDS] and having an equal Si / Al molar ratio to 3, and other poly (sialates) of Si / Al ratio> 3, the aforementioned poly (sialates) comprising an alkali metal cation M chosen from K, Na, Li, Cs and one of their mixtures, and n denotes the degree of polymerization.
Dans un mode de réalisation, le matériau géopolymère représente de 5 à 98% en poids environ, de préférence de 55 à 95% en poids environ, et de préférence encore de 65 à 90% en poids environ, par rapport au poids total de la couche composite. In one embodiment, the geopolymer material represents from 5 to 98% by weight approximately, preferably from 55 to 95% by weight approximately, and more preferably from 65 to 90% by weight approximately, relative to the total weight of the composite layer.
Selon une forme de réalisation préférée de l'invention, le matériau fibreux non tissé représente de 2 à 95% en poids environ, de façon particulièrement préférée de 5 à 45% en poids environ, et encore plus préférentiellement de 10 à 35% en poids environ, par rapport au poids total de la couche composite. According to a preferred embodiment of the invention, the nonwoven fibrous material represents from 2 to 95% by weight approximately, particularly preferably from 5 to 45% by weight approximately, and even more preferably from 10 to 35% by weight approximately, relative to the total weight of the composite layer.
Selon une forme de réalisation préférée de l'invention, le gel représente de 0,1 à 15% en poids environ, de façon particulièrement préférée de 1 à 10% en poids environ, et encore plus préférentiellement de 2 à 6% en poids environ, par rapport au poids total de la couche composite. According to a preferred embodiment of the invention, the gel represents from 0.1 to 15% by weight approximately, particularly preferably from 1 to 10% by weight approximately, and even more preferably from 2 to 6% by weight approximately , relative to the total weight of the composite layer.
Avantageusement, le câble obtenu selon un procédé conforme à l'invention satisfait à au moins une des normes de réaction ou non-propagation au feu choisies parmi les normes EN 60332-1, EN 60332-3, et EN 50399 (2012/02 + Al 2016) ; et de préférence à la norme EN 50399 (2012/02 + Al 2016), en particulier aux critères de classification B2ca, sla, dO, al de ladite norme, et éventuellement aux normes EN 60332-1 et EN 60332-3. Advantageously, the cable obtained according to a process in accordance with the invention satisfies at least one of the standards for reaction or non-propagation to fire chosen from standards EN 60332-1, EN 60332-3, and EN 50399 (2012/02 + Al 2016); and preferably to standard EN 50399 (2012/02 + Al 2016), in particular the B2ca, sla, dO, al classification criteria of said standard, and possibly the EN 60332-1 and EN 60332-3 standards.
Selon une forme de réalisation de l'invention, le câble est un câble d'énergie et/ou de télécommunication, et de préférence un câble électrique. According to one embodiment of the invention, the cable is an energy and / or telecommunications cable, and preferably an electric cable.
Lorsque le câble comprend une pluralité d'éléments électriquement conducteurs allongés, la couche composite peut alors entourer la pluralité d'éléments électriquement conducteurs allongés du câble. When the cable includes a plurality of elongated electrically conductive elements, the composite layer may then surround the plurality of elongate electrically conductive elements of the cable.
Le câble peut comprendre une seule couche composite telle que définie dans l'invention ou une pluralité de couches composites telles que définies dans l'invention. The cable can comprise a single composite layer as defined in the invention or a plurality of composite layers as defined in the invention.
De préférence, le câble comprend une seule couche composite, et de façon plus particulièrement préférée une seule couche composite interne. Preferably, the cable comprises a single composite layer, and more particularly preferably a single internal composite layer.
Selon une forme de réalisation de l'invention, le câble obtenu selon le procédé de l'invention comprend en outre un ou plusieurs couches interposées entre l'élément électriquement conducteur allongé et la couche composite telle que définie dans l'invention. According to one embodiment of the invention, the cable obtained according to the method of the invention further comprises one or more layers interposed between the elongated electrically conductive element and the composite layer as defined in the invention.
Ces couches peuvent comprendre une ou plusieurs couches polymères telles que des couches polymères électriquement isolantes. These layers can include one or more polymer layers such as electrically insulating polymer layers.
Dans ce cas, le procédé comprend en outre, avant l'étape iii), une ou plusieurs étapes d'application d'une ou plusieurs des couches mentionnées ci- dessus, autour de l'élément électriquement conducteur allongé, de l'ensemble des éléments électriquement conducteurs allongés, ou autour de chacun des éléments électriquement conducteurs allongés, selon le type de câble souhaité. In this case, the method further comprises, before step iii), one or more steps of applying one or more of the layers mentioned above, around the elongated electrically conductive element, of all of the layers. elongated electrically conductive elements, or around each of the elongated electrically conductive elements, depending on the type of cable desired.
Selon une forme de réalisation préférée de l'invention, le câble comprend : According to a preferred embodiment of the invention, the cable comprises:
- une pluralité d'éléments électriquement conducteurs, chacun desdits éléments électriquement conducteurs étant entouré par une couche polymère, notamment électriquement isolante, pour former une pluralité d'éléments électriquement conducteurs isolés, a plurality of electrically conductive elements, each of said electrically conductive elements being surrounded by a polymer layer, in particular electrically insulating, to form a plurality of isolated electrically conductive elements,
- une couche composite telle que définie dans l'invention entourant ladite pluralité d'éléments électriquement conducteurs isolés, et - une gaine externe de protection, notamment électriquement isolante, entourant ladite couche composite. a composite layer as defined in the invention surrounding said plurality of insulated electrically conductive elements, and an outer protective sheath, in particular electrically insulating, surrounding said composite layer.
Le procédé conforme à l'invention est de préférence un procédé continu. En d'autres termes, au moins les étapes i), ii) et a), et de préférence au moins les étapes iO), i), ii), a) et iii) sont effectuées en continu. The process according to the invention is preferably a continuous process. In other words, at least steps i), ii) and a), and preferably at least steps iO), i), ii), a) and iii) are carried out continuously.
Dans l'invention, l'expression "procédé continu" signifie que le procédé est effectué sur une seule ligne de production, et/ou sans étapes de repos, de recueil, ou de récupération. En d'autres termes, dans le procédé conforme à l'invention, il n'y a pas d'étapes intermédiaires de repos entre la distribution du matériau fibreux non tissé et la récupération/obtention du câble final. Plus particulièrement, les étapes i), ii) et a), ou les étapes iO), i), ii), a), et iii) sont concomitantes, i.e. les étapes i), ii) et a), ou les étapes iO), i), ii), a), et iii) sont mises en oeuvre en même temps. In the invention, the expression “continuous process” means that the process is carried out on a single production line, and / or without stages of rest, collection, or recovery. In other words, in the process according to the invention, there are no intermediate stages of rest between the distribution of the nonwoven fibrous material and the recovery / obtaining of the final cord. More particularly, steps i), ii) and a), or steps iO), i), ii), a), and iii) are concomitant, ie steps i), ii) and a), or steps iO), i), ii), a), and iii) are implemented at the same time.
Selon ce mode de réalisation, le matériau fibreux non tissé peut être disposé sur un distributeur tel qu'un dérouleur ou dévidoir, et ledit matériau peut être distribué ou déroulé en continu pour mettre en oeuvre au moins les étapes i) et iii). According to this embodiment, the nonwoven fibrous material may be placed on a dispenser such as an unwinder or unwinder, and said material may be dispensed or unwound continuously in order to carry out at least steps i) and iii).
De préférence, le matériau fibreux non tissé sous la forme d'un ruban délivré par le dérouleur ou dévidoir passe dans le dispositif de resserrement ou de conformation au travers duquel un câble comprenant au moins un élément électriquement conducteur allongé défile selon l'étape iii-v2), puis le câble ainsi obtenu passe dans le bain ou bac d'imprégnation comprenant la composition géopolymère selon l'étape i-v2), puis le câble ainsi imprégné sort du bac d'imprégnation et rentre dans la cellule de pulvérisation pour mettre en oeuvre les étapes a) et ii), puis le câble obtenu passe dans le dispositif de resserrement avant d'entrer dans la tête d'extrudeuse, afin de permettre l'extrusion de la gaine polymère autour du câble selon l'étape iv). Preferably, the nonwoven fibrous material in the form of a ribbon delivered by the unwinder or unwinder passes into the tightening or shaping device through which a cable comprising at least one elongated electrically conductive element passes according to step iii- v2), then the cable thus obtained passes into the bath or impregnation tank comprising the geopolymer composition according to step i-v2), then the cable thus impregnated leaves the impregnation tank and enters the spray cell to put carrying out steps a) and ii), then the cable obtained passes through the tightening device before entering the extruder head, in order to allow the extrusion of the polymer sheath around the cable according to step iv) .
Le distributeur délivre le matériau fibreux non tissé à une vitesse V (en km/min). The distributor delivers the nonwoven fibrous material at a speed V (in km / min).
La vitesse V est de préférence identique à la vitesse de défilement du câble. De préférence, le bain ou bac d'imprégnation est alimenté avec la composition géopolymère avec un débit D (en kg/min). Le débit D peut aller de 0,5 kg/min à 4,5 kg/min environ. The speed V is preferably identical to the running speed of the cable. Preferably, the impregnation bath or tank is supplied with the geopolymer composition at a flow rate D (in kg / min). The flow rate D can range from 0.5 kg / min to 4.5 kg / min approximately.
La vitesse de défilement du câble dans le procédé va de 20 m/min à 280 m/min environ, et de préférence va de 50 m/min à 150 m/min environ. The cable running speed in the process ranges from approximately 20 m / min to 280 m / min, and preferably ranges from approximately 50 m / min to 150 m / min.
Brève description des dessins Brief description of the drawings
Les dessins annexés illustrent l'invention : The accompanying drawings illustrate the invention:
La Figure 1 représente une vue schématique en coupe d'un câble électrique tel qu'obtenu selon le procédé conforme à l'invention. Figure 1 shows a schematic sectional view of an electric cable as obtained according to the process according to the invention.
La Figure 2 représente une vue schématique du procédé conforme à l'invention selon un mode de réalisation. FIG. 2 represents a schematic view of the method according to the invention according to one embodiment.
Pour des raisons de clarté, seuls les éléments essentiels pour la compréhension de l’invention ont été représentés de manière schématique sur ces figures, et ceci sans respect de l’échelle. For reasons of clarity, only the elements essential for an understanding of the invention have been shown schematically in these figures, and this without respecting the scale.
Le câble électrique 10A, illustré sur la figure 1, correspond à un câble électrique résistant au feu de type K25 ou RZ1K. The 10A electric cable, illustrated in figure 1, corresponds to a fire-resistant electric cable of type K25 or RZ1K.
Ce câble électrique 10 comprend quatre éléments électriquement conducteurs allongés 1, chacun étant isolé avec une couche électriquement isolante 200, et, successivement et coaxialement autour de ces quatre éléments électriquement conducteurs allongés isolés (100, 200), une couche composite 3 telle que définie dans l'invention entourant les quatre éléments électriquement conducteurs allongés isolés (100, 200), et une gaine externe 400 de type HFFR entourant la couche composite 300 telle que définie dans l'invention, et se présente avantageusement sous la forme d'un ruban. This electric cable 10 comprises four elongated electrically conductive elements 1, each being insulated with an electrically insulating layer 200, and, successively and coaxially around these four isolated elongated electrically conductive elements (100, 200), a composite layer 3 as defined in the invention surrounding the four elongated insulated electrically conductive elements (100, 200), and an outer sheath 400 of the HFFR type surrounding the composite layer 300 as defined in the invention, and is advantageously in the form of a ribbon.
Les exemples suivants permettent d’illustrer la présente invention. Ils n’ont pas de caractère limitatif sur la portée globale de l’invention telle que présentée dans les revendications. The following examples illustrate the present invention. They are not limiting on the overall scope of the invention as set out in the claims.
EXEM PLE EXAMPLE
Sur la figure 2, est illustrée une vue schématique du procédé conforme à l'invention mis en oeuvre de façon continue. En particulier, un matériau fibreux non tissé 1 sous la forme d'un ruban est placé sur un enrouleur 2, déroulé et amené jusqu'à un dispositif de resserrement 3 au travers duquel un câble comprenant au moins un élément électriquement conducteur allongé 4 (câble nu 4) défile, afin de permettre l'enroulement longitudinal du ruban 1 autour du câble 4 [étape iii-v2)] Puis, le câble obtenu comprenant l'élément électriquement conducteur allongé et ledit matériau fibreux non tissé entourant ledit élément électriquement conducteur allongé 5 passe dans un bain d'imprégnation 6 comprenant une composition géopolymère 7, afin de permettre l'imprégnation du matériau fibreux non tissé 1 par ladite composition géopolymère 7 [étape i- v2)]. Le câble imprégné 8 obtenu passe alors dans une cellule de pulvérisation 9 comprenant une chambre tubulaire et des tubulures permettant la pulvérisation d'une composition gélifiante 1 0 comprenant 10 g d'un alginate et 1 g de chlorure de calcium sur le câble imprégné 8 [étapes a) et il)] . En sortie de cellule de pulvérisation 9, le câble obtenu 1 1 entre dans un dispositif de resserrement 1 2 connecté à ladite chambre tubulaire et est amené vers une tête d'extrudeuse 1 3, afin de permettre l'extrusion de la gaine polymère autour du câble pour former un câble gainé 14 [étape iv)]. In FIG. 2, a schematic view of the process according to the invention implemented continuously is illustrated. In particular, a nonwoven fibrous material 1 in the form of a tape is placed on a winder 2, unwound and brought to a tightening device 3 through which a cable comprising at least one elongated electrically conductive element 4 (bare cable 4) runs, in order to allow the longitudinal winding of the tape 1 around the cable 4 [step iii-v2) ] Then, the cable obtained comprising the elongated electrically conductive element and said nonwoven fibrous material surrounding said elongated electrically conductive element 5 passes into an impregnation bath 6 comprising a geopolymer composition 7, in order to allow the impregnation of the non-fibrous material. woven 1 by said geopolymer composition 7 (step i-v2)]. The impregnated cable 8 obtained then passes into a spraying cell 9 comprising a tubular chamber and pipes allowing the spraying of a gelling composition 1 0 comprising 10 g of an alginate and 1 g of calcium chloride on the impregnated cable 8 [ steps a) and ii)]. At the outlet of the spray cell 9, the cable obtained 1 1 enters a tightening device 1 2 connected to said tubular chamber and is brought to an extruder head 1 3, in order to allow the extrusion of the polymer sheath around the cable to form a sheathed cable 14 [step iv)].
La couche composite obtenue est sèche et peut se déformer tout en conservant sa cohésion sans aucun déchirement. Des tests de vieillissement montrent que les étapes a) et ii) permettent de conserver les propriétés de flexibilité après un vieillissement prolongé en température contrairement à la mise oeuvre d'un procédé sans étapes a) et ii). Les propriétés feu ne sont pas altérées puisque les essais feu selon la norme EN50399 restent inchangées B2, si, dl. The composite layer obtained is dry and can be deformed while retaining its cohesion without any tearing. Aging tests show that steps a) and ii) make it possible to retain the flexibility properties after prolonged temperature aging, unlike the implementation of a process without steps a) and ii). The fire properties are not altered since the fire tests according to standard EN50399 remain unchanged B2, si, dl.

Claims

Revendications Claims
1. Procédé de fabrication d'un câble comprenant au moins un élément électriquement conducteur allongé et au moins une couche composite entourant ledit élément électriquement conducteur allongé, caractérisé en ce qu'il comprend au moins les étapes suivantes : i) imprégner un matériau fibreux non tissé, de préférence sous la forme d'un ruban ou d'une bande, avec une composition géopolymère liquide, et ii) former un gel encapsulant ou supportant ledit matériau fibreux non tissé, ledit gel comprenant un matériau géopolymère, et en ce que ledit procédé comprend en outre une étape a) d'ajout d'une composition gélifiante à la composition géopolymère liquide, pour former ledit gel lors de l'étape ii). 1. A method of manufacturing a cable comprising at least one elongated electrically conductive element and at least one composite layer surrounding said elongated electrically conductive element, characterized in that it comprises at least the following steps: i) impregnating a non-fibrous material. woven, preferably in the form of a sliver or band, with a liquid geopolymeric composition, and ii) forming a gel encapsulating or supporting said nonwoven fibrous material, said gel comprising a geopolymeric material, and in that said method further comprises a step a) of adding a gelling composition to the liquid geopolymer composition, to form said gel during step ii).
2. Procédé selon la revendication 1, caractérisé en ce que la composition géopolymère liquide comprend au moins un premier aluminosilicate, au moins un premier silicate alcalin, de l'eau, et éventuellement une base alcaline. 2. Method according to claim 1, characterized in that the liquid geopolymer composition comprises at least a first aluminosilicate, at least a first alkali silicate, water, and optionally an alkaline base.
3. Procédé selon la revendication 1 ou 2, caractérisé en ce que le matériau fibreux non tissé est choisi parmi les matériaux cellulosiques, les matériaux à base de polymères organiques synthétiques, les fibres de verre, et un de leurs mélanges. 3. Method according to claim 1 or 2, characterized in that the nonwoven fibrous material is chosen from cellulosic materials, materials based on synthetic organic polymers, glass fibers, and a mixture thereof.
4. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'étape i) est effectuée sur le matériau fibreux non tissé seul selon l'étape i-vl), et ladite étape i-vl) est effectuée par enduction imprégnation. 4. Method according to any one of the preceding claims, characterized in that step i) is carried out on the nonwoven fibrous material alone according to step i-vl), and said step i-vl) is carried out by coating impregnation.
5. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que l'étape i) est effectuée sur un ensemble matériau fibreux non tissé/câble comprenant au moins un élément électriquement conducteur allongé selon l'étape i-v2), et ladite étape i-v2) est effectuée par trempage enduction. 5. Method according to any one of claims 1 to 3, characterized in that step i) is carried out on a nonwoven fibrous material / cable assembly comprising at least one electrically conductive element elongated according to step i-v2) , and said step i-v2) is carried out by coating soaking.
6. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'étape a) d'ajout d'une composition gélifiante est effectuée avant l'étape i) ou après l'étape i) d'imprégnation du matériau fibreux non tissé. 6. Method according to any one of the preceding claims, characterized in that step a) of adding a gelling composition is carried out before step i) or after step i) of impregnating the fibrous material. nonwoven.
7. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la composition gélifiante comprend au moins un composé précurseur d'un gel choisi parmi les polymères organiques réticulables, les polysaccharides, les monomères organiques, et un de leurs mélanges. 7. Method according to any one of the preceding claims, characterized in that the gelling composition comprises at least one precursor compound of a gel chosen from crosslinkable organic polymers, polysaccharides, organic monomers, and one of their mixtures.
8. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la composition gélifiante comprend en outre un agent de réticulation et/ou un catalyseur de réticulation et/ou un initiateur. 8. Method according to any one of the preceding claims, characterized in that the gelling composition further comprises a crosslinking agent and / or a crosslinking catalyst and / or an initiator.
9. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le composé précurseur d'un gel est choisi parmi les alginates et les amidons. 9. Method according to any one of the preceding claims, characterized in that the precursor compound of a gel is chosen from alginates and starches.
10. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le composé précurseur d'un gel est un polysaccharide sous la forme d'une poudre. 10. Method according to any one of the preceding claims, characterized in that the precursor compound of a gel is a polysaccharide in the form of a powder.
11. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'ajout de la composition gélifiante a) est effectué par pulvérisation d'une poudre de la composition gélifiante dans la composition géopolymère liquide ; ou par mélange d'une composition gélifiante liquide avec la composition géopolymère liquide. 11. Method according to any one of the preceding claims, characterized in that the addition of the gelling composition a) is carried out by spraying a powder of the gelling composition into the liquid geopolymer composition; or by mixing a liquid gelling composition with the liquid geopolymer composition.
12. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'étape ii) est concomitante avec l'étape a). 12. Method according to any one of the preceding claims, characterized in that step ii) is concomitant with step a).
13. Procédé selon l'une quelconque des revendications 1 à 11, caractérisé en ce que l'étape ii) est réalisée après l'étape a), et l'étape ii) est mise en oeuvre en présence d'un stimulus externe. 13. Method according to any one of claims 1 to 11, characterized in that step ii) is carried out after step a), and step ii) is carried out in the presence of an external stimulus.
14. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le procédé est continu. 14. Method according to any one of the preceding claims, characterized in that the method is continuous.
15. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il comprend en outre une étape iii) d'application du matériau fibreux non tissé autour d'un câble comprenant au moins un élément électriquement conducteur allongé. 15. Method according to any one of the preceding claims, characterized in that it further comprises a step iii) of applying the nonwoven fibrous material around a cable comprising at least one elongated electrically conductive element.
EP21740129.8A 2020-06-19 2021-06-17 Method for manufacturing a fire-resistant and/or fire-retardant cable Pending EP4168621A1 (en)

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FR3030100B1 (en) * 2014-12-10 2018-03-02 Nexans CABLE OR ACCESSORY FOR CABLE COMPRISING A FIRE RESISTANT LAYER
KR20160074864A (en) 2014-12-18 2016-06-29 주식회사 케이오씨솔루션 Reinforced plastic sheet and a method of preparing it

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