EP1905046B1 - Electric insulator and a method for the production thereof - Google Patents

Electric insulator and a method for the production thereof Download PDF

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Publication number
EP1905046B1
EP1905046B1 EP06792535.4A EP06792535A EP1905046B1 EP 1905046 B1 EP1905046 B1 EP 1905046B1 EP 06792535 A EP06792535 A EP 06792535A EP 1905046 B1 EP1905046 B1 EP 1905046B1
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EP
European Patent Office
Prior art keywords
tube
fibers
mixture
mineral filler
insulator
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EP06792535.4A
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German (de)
French (fr)
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EP1905046A1 (en
Inventor
Jean-Luc Bessede
Yannick Kieffel
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General Electric Technology GmbH
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Alstom Technology AG
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes epoxy resins

Definitions

  • the present invention relates to an electrical insulator comprising a tube surrounded by an insulating sheath.
  • the sheath may be smooth or have fins.
  • the present invention also relates to a method of manufacturing this insulator.
  • the insulator of the present invention can be used in particular in high and medium voltage external applications, that is to say greater than 1000 V.
  • Polymer insulators especially for outdoor applications, are made of expensive materials and complex processes.
  • the usual methods use a central tube made of resin, for example epoxy, reinforced with fibers, for example glass.
  • the tube imparts mechanical strength to the insulator.
  • the outer surface of the tube is covered with a layer of insulating material, called the sheath, to provide the surface with its electrical properties required for example for high voltage insulators, and to protect the tube from the weather, moisture and humidity. arcing on the surface of the insulator.
  • the surface of the insulator is usually formed so as to have a series of fins which provide an extended escape distance.
  • the insulator has a smooth sheath, especially in the case of insulator for indoor use.
  • sheath designates both a smooth sheath and a sheath comprising fins.
  • fins means a sheath made of fins.
  • Mainly four techniques are used to form the sheath of an insulator and its fins: (1) direct molding on the tube, (2) manufacturing fins and then attaching them to the tube, (3) forming a band and which is then surrounded around the tube, (4) extrusion of the fins directly on the tube by means of a screw-shaped mold.
  • the technique (1) requires the formation of a special mold for the fins, the techniques (2) to (4) require a post-treatment of cross-linking of the fins.
  • all techniques (1) to (4) generally use silicone-based materials because of their hydrophobicity.
  • silicone or "silicone rubber” a composite elastomeric material composed of silicone polymer resin, single-component or two-component, optionally reinforced with a mineral filler.
  • the document EP-A-1091365 [1] discloses an insulator made of a fiber reinforced epoxy tube and surrounded by an insulating protection made of silicone rubber. This protection may be in the form of fins.
  • the insulator can be obtained by molding the vulcanized silicone rubber on the fiber reinforced epoxy tube. Silicone is used for its hydrophobicity and hydrophobicity transfer properties.
  • insulators however, have an interface of two different materials between the tube and the fins, which can cause voids and delamination phenomena due to different coefficients of thermal expansion, and leads, when using these insulators to partial discharges and subsequently to breakdowns.
  • the document WO 02/061767 [2] describes a housing for an electrical appliance.
  • This shell comprises a tube called sheath, at least one fin, and a hydrophobic coating disposed on the fin.
  • the tube is made of high temperature silicone vulcanization (type “HTV” for "High Temperature Vulcanising "), the silicone fin consists of room temperature vulcanizing silicone (“ RTV “type) and the hydrophobic coating of liquid silicone rubber (“ LS rubber ”) and silicone RTV. Liquid silicone is molded, and solid silicone is extruded.
  • any defect of the fins will be a point of weakness for the holding in time of the insulator.
  • fins may be torn when the insulator is resting on an angled portion.
  • the silicone can be attacked by animals, such as birds or rodents.
  • the resins used in this document do not make it possible to overcome all of the disadvantages described above: they do not withstand external aggression in operation (rodents, birds, rain, pollution, etc.), tracking, and the like. erosion (class 1B3 resin, according to IEC 60587). In addition, they do not withstand handling in the factory, mounting on site, cut or tear when opening packages. Indeed, these materials have mechanical characteristics similar to silicone. Thus, the same problems can be expected during the manufacturing process of the insulator, in assembly for its use as an insulator and in operation.
  • the document GB-A-2,147,225 discloses an electrical insulator in which the insulating material comprises a resin which is not a flexibilized resin but rather a rigid, brittle resin.
  • the document US Patent 3,645,899 relates to an electrical insulator consisting of a monolithic mass of an insulating material comprising a charged, cured epoxy resin.
  • the insulation is in the form of a block and not a sheath.
  • the present invention specifically relates to an electrical insulator that meets this and other needs.
  • the electrical insulator of the present invention is defined in claim 1. It comprises a hollow or solid tube surrounded by a insulating sheath.
  • the insulating sheath may be smooth or finned.
  • the insulator of the present invention is characterized in that the insulating sheath is made of a hardened charged flexibilized hydrophobic cycloaliphatic epoxy resin obtained by curing a mixture comprising: from 25 to 75% by weight of mineral filler, preferably 30 to 70% by weight of mineral filler, preferably 40 to 60% by weight of inorganic filler, more preferably 45 to 55% by weight of inorganic filler, for example 50% by weight, a hydrophobic cycloaliphatic epoxy resin and a hardener.
  • a hardened charged flexibilized hydrophobic cycloaliphatic epoxy resin obtained by curing a mixture comprising: from 25 to 75% by weight of mineral filler, preferably 30 to 70% by weight of mineral filler, preferably 40 to 60% by weight of inorganic filler, more preferably 45 to 55% by weight of inorganic filler, for example 50% by weight, a hydrophobic cycloaliphatic epoxy resin and a hardener.
  • charged resin is understood to mean a composite material composed of an epoxy resin, a hardener and a mineral filler.
  • the role of the mineral filler is to improve the mechanical properties of the hardened resin as well as its resistance to erosion and electrical flow.
  • the cured filled resin of the present invention is a so-called "flexibilized” resin.
  • this resin once polymerized, has particular mechanical properties such as a very high modulus of elasticity and deformation at break, namely a modulus of elasticity ranging from 200 to 4000 MPa and a deformation at break ranging from 10 to 30%.
  • This hardened filled resin is generally obtained by mixing a specially formulated base resin to obtain, at the end of the hardening process, a flexibilised hardened resin, hardener (s) specially formulated for the purpose of obtaining a flexibilised hardened resin and possible additives such as flexibilizers (these two or even three elements chemically reacting together, to obtain a flexibilized hardened resin), as well as mineral fillers.
  • the term "flexibilized resin” is a term commonly used in this field of the art and whose meaning is perfectly clear and unambiguous to those skilled in the art. Flexibility of the resins can be achieved by chemically modifying the hardener and potentially resin molecules, and / or potentially incorporating flexibilizer (flexible chains such as aliphatic chains) upon polymerization.
  • a flexibilized resin may have a reduced degree of crosslinking with respect to this resin prior to any flexibilization treatment.
  • the flexibilization of a cured resin is obtained mainly by modifying the cycloaliphatic hardener by removing the two reactive aliphatic rings by insertion of an aliphatic chain.
  • the cured loaded flexibilized cycloaliphatic epoxy resin of the present invention has a modulus of elasticity of 200 to 4000 MPa.
  • the cured loaded flexibilized hydrophobic cycloaliphatic epoxy resin used in the present invention has a glass transition temperature of 0 to 50 ° C, preferably 10 to 30 ° C, more preferably 18 to 30 ° C, a modulus of elasticity from 200 to 4000 MPa; an elongation at break of 10 to 30%; a breaking stress of 14 to 40 MPa: and in addition a shore A hardness greater than 98, and / or a resistance to tracking and erosion of class 1A3.5 or 1B3.5 or higher according to the standard IEC 60587.
  • the inorganic filler preferably comprises 25 to 75% by weight of alumina trihydrate (ATH) (Al (OH) 3 ), preferably 40 to 60% by weight, for example 50% by weight, the remainder being at least one other mineral filler material.
  • ATH alumina trihydrate
  • Al (OH) 3 alumina trihydrate
  • the other inorganic filler material may advantageously be chosen from the group comprising alumina (Al 2 O 3 ), silica (SiO 2 ), calcium oxide (CaO), magnesium (MgO), zinc oxide (ZnO), silicon fluoride, wollastonite, calcium carbonate (CaCO 3 ), oxide titanium (TiO 2 ), clay nanoparticles or a mixture of two or more thereof.
  • the other filler material is alumina or silica or a mixture of alumina and silica.
  • the inorganic filler comprises from 25 to 75% by weight of alumina trihydrate, preferably from 40 to 60% by weight of alumina trihydrate, for example 50% by weight, the remainder consisting of alumina or silica or a mixture of alumina and silica.
  • this mixture may consist, for example, of from 1 to 99% by weight of alumina, for example from 5 to 95% by weight of alumina, for example from 30 to 70% by weight. % by weight of alumina, the remainder being silica.
  • the mineral filler is preferably composed of particles of different particle sizes: particles of one or more of the chemical types mentioned above (mineral filler) of submicron size and particles of one or more chemical types among those mentioned above (mineral filler) of micron size, these reinforcing particles of different sizes may be of identical or different chemical composition.
  • the inorganic filler may be a mixture of micron-size filler and submicron size.
  • the micron-size particles may be of several different chemical compositions, as well as the submicron-sized particles.
  • the particles of submicron size have a size at least twice as much small as the size of micron sized particles.
  • the notion of size refers to the "median diameter" of the particle distribution in the case where the particles used have a geometry close to the spherical geometry. It is recalled that the "median diameter” is the diameter of the particle at the median of the particle diameter distribution, the median representing the value where the total frequency of the values above and the total frequency below that value. value are identical. In the case where the particles used have morphologies with strong form factors, for example lamellar morphologies such as leaflets or rods, the notion of size then relates to the largest dimension of the particle, for example the length in the case of a leaflet.
  • the size of the particles of submicron size is less than or equal to one micrometer, and that the size of the micron-sized particles is greater than one micrometer.
  • the micron-sized particles have a size of between 1 and 30 microns and the particles of submicron size have a size of less than 1 micrometer.
  • the particles of submicron size have a size of a few hundred nanometers and a minimum of 5 nanometers.
  • the particles of the mineral filler (s) are surface-chemically treated to improve wetting and adhesion with the epoxy resin.
  • the silica is modified by silanization.
  • the mixture which, after curing, makes it possible to obtain a hardened charged flexibilized hydrophobic cycloaliphatic epoxy resin comprises an unmodified hydrophobic cycloaliphatic base epoxy resin.
  • said mixture also comprises a hardener.
  • a hardener Any of the cycloaliphatic epoxy resin hardeners known to those skilled in the art can be used to practice the present invention. It may be for example a cycloaliphatic anhydride. The amount of this hardener is generally 60 to 100% by weight based on the total mass of the unloaded resin used in the present invention.
  • the hardener can be chemically modified to flexibilize the resin once cured.
  • This component is known as a flexibilizer hardener.
  • said mixture may comprise chemical additives including flexibilizers, accelerators, one or more specific additives making it possible to make the resin hydrophobic chosen from an -OH-terminated polysiloxane, a polysiloxane / polyether copolymer and a polysiloxane cyclic or a mixture of two or three of these polysiloxanes
  • said mixture may further comprise elastomeric spheres.
  • elastomeric spheres are added at a rate of 5 to 10% by weight of elastomeric spheres. This percentage is of course expressed relative to the weight of the hydrophobic cycloaliphatic epoxy resin loaded.
  • These spheres absorb the energy of shocks that may suffer the insulator.
  • These may be, for example, Durastrength Impact Modifier spheres (trademark) marketed by Arkema.
  • said mixture may further comprise one or more additive (s) chosen from an -OH-terminated polysiloxane, a polysiloxane / polyether copolymer and a cyclic polysiloxane or a mixture of two or three of these polysiloxanes. . More specifically, it may be for example dodecamethylcyclohexasiloxane.
  • the amount of this or these additive (s) is generally from 1 to 10% by weight relative to the total mass of the filled resin used in the present invention.
  • the inorganic filler is preferably desiccated and degassed before being mixed with the epoxy resin to form the hydrophobic cycloaliphatic epoxy resin used in the present invention. Indeed, this makes it possible to improve the dispersion of the filler in the resin and to obtain a homogeneous mixture.
  • This drying and degassing can be carried out simultaneously, for example by placing the mineral filler under vacuum at a temperature of 70 to 100 ° C, for example for 10 to 30 hours.
  • the cured loaded flexibilized hydrophobic cycloaliphatic epoxy resin used in the present invention can be prepared by simply mixing the uncured resin, the filler and the hardener and any additives.
  • this mixture is of course designed so as to obtain a homogeneous mixture, that is to say a homogeneous dispersion of the mineral filler and hardener and any additives in the resin.
  • a part of the inorganic filler is mixed with the liquid resin (that is to say uncured resin), another part of the mineral filler, preferably dried and degassed, is mixed with liquid hardener, and the two mixtures obtained are mixed together to form a filled resin for use in the present invention.
  • the liquid resin that is to say uncured resin
  • another part of the mineral filler preferably dried and degassed
  • liquid hardener is mixed with liquid hardener, and the two mixtures obtained are mixed together to form a filled resin for use in the present invention.
  • each mixture is made at a temperature of 40 to 60 ° C and degassed.
  • the mixtures can be made mechanically, for example in the form of kneading.
  • the insulator of the present invention also includes a tube.
  • the insulator tube may be a solid or hollow tube. It gives the insulator its mechanical strength. It can be flexible or rigid. Preferably, it is rigid.
  • the geometry of the tube is not limited to a particular shape. It is chosen in particular according to the intended application. It may be for example a tube chosen from a straight tube, a conical tube, a frustoconical tube, a barrel-shaped tube, etc. or a tube having a combination of these different shapes or geometries. Most often, the tube is straight, or conical or frustoconical or barrel-shaped.
  • the section of the tube is also not limited to a particular geometry. It is chosen in particular according to the intended application. It is most commonly round, but it can also be square, triangular, polygonal, for example from 5 to 30 sides. The ease of its manufacture can also be a criterion for choosing the geometry of the tube and its section.
  • the tube may for example be a thermosetting polymer or thermoplastic resin tube reinforced with short or long fibers of mineral or organic chemical nature.
  • Short fibers are fibers of average length less than 30 mm.
  • long fibers are meant fibers of average length greater than 30 mm.
  • the tube is made by injection. The injection points are defined so as to obtain a good alignment of the fibers parallel to the axis of the tube.
  • the tube may advantageously be formed from a tube-shaped fiber arrangement.
  • These fibers can be long or short.
  • the fiber arrangement can be formed for example by filament winding of long fibers or from short fibers.
  • a fiber arrangement it may consist for example of a fiber arrangement selected from a fiber mat or a fabric of one-dimensional, two-dimensional or three-dimensional fibers.
  • the fiber arrangement may be in woven or nonwoven form.
  • the fibers are preferably chosen from mineral fibers such as glass fibers, quartz fibers, silicon carbide fibers, or from organic fibers such as aramid fibers, e.g. kevlar (trade mark), polyester fibers, and polybenzobisoxazole fibers, e.g. zylon (trademark).
  • mineral fibers such as glass fibers, quartz fibers, silicon carbide fibers
  • organic fibers such as aramid fibers, e.g. kevlar (trade mark), polyester fibers, and polybenzobisoxazole fibers, e.g. zylon (trademark).
  • the fibers of the arrangement are preferably impregnated with an epoxy resin, and more preferably with a cycloaliphatic epoxy resin, for example a hydrophobic cycloaliphatic epoxy resin loaded with an organic or inorganic particulate reinforcement (such as alumina, silica or a mixture of both) according to the present invention, as defined above.
  • a cycloaliphatic epoxy resin for example a hydrophobic cycloaliphatic epoxy resin loaded with an organic or inorganic particulate reinforcement (such as alumina, silica or a mixture of both) according to the present invention, as defined above.
  • the fiber arrangement is impregnated with hydrophobic cycloaliphatic epoxy resin comprising from 25 to 75% by weight mineral filler and a hardener.
  • the fibers may have / be subjected to a specific surface treatment in order to improve their compatibility with the impregnating resin, in particular the wettability of the resin on the fibers.
  • the fiber arrangement thus constitutes a precursor of the insulator tube of the present invention.
  • the tube may be for example a thermosetting or thermoplastic polymeric resin tube reinforced with inorganic or organic filler, for example an epoxy resin tube reinforced with alumina or silica.
  • the present invention relates generally to the use, as defined in claim 29, of a cured loaded flexibilized hydrophobic cycloaliphatic epoxy resin obtained by curing a mixture comprising from 25 to 75% by weight of inorganic filler, preferably from 30 to 70% by weight of mineral filler, preferably from 40 to 60% by weight of inorganic filler, more preferably from 45 to 55% by weight of inorganic filler, for example 50% by weight, an epoxy resin hydrophobic cycloaliphatic and a hardener for the manufacture of an electrical insulator, in particular for the manufacture of the outer sheath of an insulator, this sheath may be provided with fins or not.
  • the loaded flexibilized hydrophobic cycloaliphatic epoxy resin cured in the course of this use has the same properties as those obtained above.
  • the mineral filler makes it possible both to improve the tracking behavior and the erosion of the material.
  • the filled resin can be used to manufacture only the sheath of the insulator, provided or not with fins, for example to replace the silicone-based materials of the prior art, or to manufacture the tube, the sheath and the fins of the insulator, for example when the tube consists of a fiber arrangement.
  • the present invention may for example consist of molding said fins on a tube
  • the tube may for example be constituted by an arrangement of fibers reinforced with an epoxy resin identical to or different from that used for the sheath, with or without fins.
  • the tube may be for example a tube made of fibers reinforced with an epoxy resin as described and obtained in document [1].
  • the present invention may be implemented for example in a method of manufacturing an electrical insulator comprising a hollow or solid tube surrounded by an insulating sheath, said sheath being able to be provided with fins, as defined in claim 16.
  • a precursor of the tube is used, this precursor consisting of a fiber arrangement as indicated above.
  • the precursor (fiber arrangement) is placed in the mold, said fiber arrangement being impregnated with the filled resin during the step of introducing said resin into the mold to form after curing. the resin the tube.
  • the charged resin forms the tube and the fins of the insulator.
  • a sleeve is placed in the tube formed by the fiber arrangement so that the resin does not fill the hollow tube.
  • a tube which is a resin tube reinforced with a short fiber arrangement. or long of chemical nature mineral or organic.
  • the resin is the same or different from the filled resin used to form the sheath and fins.
  • This may be for example a CEVOLIT (trademark) tube manufactured by Tyco Electronics Energy. It may be for example a tube such as that described in document [1]. This tube can be made for example as indicated in this document, and then used in the process of the present invention to manufacture the insulator.
  • the finned electric insulator mold is preferably made of a metallic material, preferably stainless steel. It is preferably of cylindrical shape and draws the fins of the insulator. More generally, it may be, as for the shape of the tube, any desired geometric shape, for example of cylindrical, conical, frustoconical or barrel shape or any other form advantageous for its use.
  • Such molds can be manufactured by machining in the mass of stainless steel using precision devices, such as digital milling machines and digital grinders.
  • An electroerosion, chemical polishing or even mechanical polishing surface treatment can make it possible to improve the surface quality of the mold, and consequently the surface quality of the insulator (low surface roughness).
  • These molds can be designed and made by companies such as Techni-Molds, REP France or FAMACOM.
  • a release agent based on silicone (s) can be used to facilitate the demolding of the insulator.
  • the release agent L 94-700 (commercial reference) from Kluber Chemie can be used.
  • the mixture is introduced into the mold by any appropriate means to fill it.
  • the mixture is injected under pressure into the mold, for example using an injection molding machine of the same type as that used to inject the silicone into the manufacture of the insulators of the prior art.
  • the mixture is injected hot, to allow it to fit more easily the shape of the mold, for example at a temperature of 100 to 140 ° C.
  • the mold is heated at this temperature, for the same reasons, during the injection of the resin.
  • the mixture is injected at several points along the insulator.
  • the hollow or solid tube for example hollow based on epoxy resin reinforced with long glass fibers, is previously arranged in the mold, and preferably maintained at the same temperature as the mold (for example 130-140 ° C.) in order to have a good adhesion of the resin on the tube.
  • the tube preferably longer than the mold, protrudes from both sides of the mold.
  • the mixture is maintained at its polymerization temperature, generally from 120 to 140 ° C., for example for a period of 4 to 10 hours.
  • the insulator obtained is removed from the mold.
  • the insulator it is possible to post-cure the insulator, for example at a temperature of 130 to 150 ° C., for example for 6 to 10 hours in order to obtain optimum mechanical characteristics of the resin.
  • the insulator obtained can undergo a finishing treatment.
  • the hollow tube can be cut to the final length of the insulator if it is too long.
  • Molding traces such as burrs at the join of the mold can be removed by mechanical action, for example by mechanical polishing.
  • one or two metal collar (s) can be fixed in a traditional manner, for example by gluing respectively to one or both ends of the insulator, for example with an epoxy adhesive.
  • the hooping technique is used in which the metal collar is expanded in temperature, which makes it possible to force the glue-in tube into the glued collar.
  • the shrinkage of the metal collar on the composite tube ensures a good adhesion of the collar on the tube. This adhesion is reinforced by the glue.
  • the method may further comprise a step of bonding one or two collar (s) respectively to one or both ends of the electrical insulator.
  • the manufactured insulator is a carrier insulator.
  • Two metal collars may be attached as described above in the case of a carrier insulator to be connected at both ends.
  • a single metal collar is attached as described above in the case of an insulator used as a single support.
  • the other end can be machined to receive the lead brought to the potential.
  • the machining can be done in the form of a notch in the case of a bar support or it can achieve a bore in the tube to pass a conductor.
  • the insulator of the present invention for example solid tube or composite / glass mat may be cylindrical, conical, barrel or any other form useful for its use.
  • Example 1 Manufacture of a hollow tube insulator according to the invention
  • the mold used is cylindrical and draws the fins of the insulator. It is steel.
  • the mold consists of two joined shells, each having an internal half insulator lengthwise. Thus, the demolding of the fin isolator can be done by simple separation of the two shells.
  • a hollow cylindrical composite tube based on glass fiber reinforced epoxy resin (in the form of fiberglass mat) is arranged centrally on the longitudinal axis of the mold.
  • the composite tube is longer than the mold, it exceeds both sides of the mold.
  • a flexibilized hydrophobic cycloaliphatic epoxy resin comprising 50% by weight mineral filler is prepared.
  • the inorganic filler composed of 50% by weight of silica and 50% by weight of alumina trihydrate (ATH) is dried under vacuum at 80 ° C for 24 hours.
  • Second step preparation of the resin and hardener:
  • Part of the mineral filler 15 parts by weight, previously dried and degassed, is incorporated to a liquid cycloaliphatic resin of the diglycidyl ester type (100 parts by weight) having a density of 1.1.
  • the resulting mixture has a density of 1.2. It is mechanically kneaded at a temperature between 40 ° C and 60 ° C and degassed under vacuum at an absolute pressure of between 1000 and 10000 Pa (between 10 and 100 March). A resin + filler by-product is obtained.
  • the balance of the inorganic filler i.e. the remaining 35 parts by weight, is incorporated into a liquid cycloaliphatic anhydride hardener (100 weight parts).
  • the mixture thus obtained has a density of about 1.9. It is mechanically kneaded at a temperature between 40 and 60 ° C and degassed as before. A hardener + filler by-product is obtained.
  • the two by-products resin + filler and hardener + filler are mechanically mixed together until a homogeneous dispersion is obtained.
  • the mixing is carried out at a temperature between 40 and 60 ° C and degassed as before.
  • the resulting mixture is ready for use to mold the insulator.
  • the previously obtained mixture is injected under pressure into the two-part mold preheated to the polymerization temperature of the resin, here between 130 ° C. and 140 ° C., using a standard injection molding machine for the silicone.
  • the temperature is homogeneous in the mold.
  • the hollow composite tube is maintained at the mold temperature (120-130 ° C) in order to have a good adhesion of the resin on the composite tube.
  • the resin is injected at several points along the insulator to properly fill the fins drawn by the mold.
  • the resin is maintained at a temperature of 130-140 ° C for a period of 20-30 minutes for curing.
  • the hollow tube insulator (1) is extracted from the mold after curing the resin by opening it. It is represented schematically on the figure 1 attached. It comprises a tube (3) surrounded by an insulating sheath (5) provided with fins (7).
  • the insulating sheath and the fins consist of the charged flexibilized hydrophobic cycloaliphatic epoxy resin prepared in this example.
  • the tube (3) consists of a fiberglass mat reinforced with epoxy resin.
  • the insulator is post-baked at 140 ° C for 8 hours to optimize the mechanical characteristics of the resin.
  • the hollow tube is then cut to the final length of the insulator.
  • Molding traces such as burrs at the join of the mold are removed by polishing.
  • One or two metal collars are then fixed in a traditional way by bonding to both ends of the insulator.
  • the number of metal clamps depends on the application of the insulator. Similarly, one end can be machined to support a conductor.
  • the insulator obtained can be used in a high voltage application.
  • Example 2 Process for manufacturing a solid-tube insulator according to the invention
  • Example 2 The same protocol as that described in Example 1 is used for the production of the charged resin and the insulator, but the hollow tube is replaced by a solid tube.
  • An electrical isolator (1) according to the present invention is obtained.
  • This insulator is represented on the figure 2 attached. It comprises the solid tube (3 ') surrounded by an insulating sheath (5) provided with fins (7).
  • the insulating sheath and the fins are made from the prepared loaded flexibilized hydrophobic cycloaliphatic epoxy resin.
  • the tube (3 ') is a rod made of epoxy resin reinforced by a fiberglass arrangement.
  • This isolator is suitable for example for use in high voltage line supports air.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Insulating Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Insulators (AREA)
  • Organic Insulating Materials (AREA)

Description

Domaine techniqueTechnical area

La présente invention se rapporte à un isolateur électrique comprenant un tube entouré d'une gaine isolante. La gaine peut être lisse ou comporter des ailettes. La présente invention se rapporte également à un procédé de fabrication de cet isolateur.The present invention relates to an electrical insulator comprising a tube surrounded by an insulating sheath. The sheath may be smooth or have fins. The present invention also relates to a method of manufacturing this insulator.

L'isolateur de la présente invention est utilisable en particulier dans les applications extérieures hautes et moyennes tensions, c'est-à-dire supérieures à 1000 V.The insulator of the present invention can be used in particular in high and medium voltage external applications, that is to say greater than 1000 V.

Dans la suite de la description, les références entre crochets ([ ]) renvoient à la liste de références présentée à la fin des exemples.In the rest of the description, references in square brackets ([]) refer to the list of references presented at the end of the examples.

Art antérieurPrior art

Les isolateurs à base de polymères, en particulier pour les applications extérieures, sont réalisés avec des matériaux coûteux et des procédés complexes. Les procédés habituels utilisent un tube central réalisé en résine, par exemple époxyde, renforcé par des fibres, par exemple de verre. Le tube confère la résistance mécanique à l'isolateur. La surface externe du tube est recouverte avec une couche de matériau isolant, appelée la gaine, pour fournir à la surface ses propriétés électriques requises par exemple pour des isolateurs à haute tension, et pour protéger le tube des intempéries, de l'humidité et des arcs électriques à la surface de l'isolateur. La surface de l'isolateur est habituellement formée de manière à présenter une série d'ailettes qui permettent d'offrir une distance de fuite étendue.Polymer insulators, especially for outdoor applications, are made of expensive materials and complex processes. The usual methods use a central tube made of resin, for example epoxy, reinforced with fibers, for example glass. The tube imparts mechanical strength to the insulator. The outer surface of the tube is covered with a layer of insulating material, called the sheath, to provide the surface with its electrical properties required for example for high voltage insulators, and to protect the tube from the weather, moisture and humidity. arcing on the surface of the insulator. The surface of the insulator is usually formed so as to have a series of fins which provide an extended escape distance.

Il existe également des applications où l'isolateur a une gaine lisse, notamment dans le cas d'isolateur destiné à une utilisation intérieure. Dans l'ensemble de la présente description, le terme « gaine » désigne aussi bien une gaine lisse qu'une gaine comprenant des ailettes. De même, le terme « ailettes » désigne une gaine composée d'ailettes.There are also applications where the insulator has a smooth sheath, especially in the case of insulator for indoor use. Throughout the present description, the term "sheath" designates both a smooth sheath and a sheath comprising fins. Similarly, the term "fins" means a sheath made of fins.

Principalement quatre techniques sont utilisées pour former la gaine d'un isolateur et ses ailettes : (1) moulage direct sur le tube, (2) fabrication des ailettes et ensuite fixation de celles-ci sur le tube, (3) formation d'une bande et qui est ensuite entourée autour du tube, (4) extrusion des ailettes directement sur le tube au moyen d'un moule en forme de vis.Mainly four techniques are used to form the sheath of an insulator and its fins: (1) direct molding on the tube, (2) manufacturing fins and then attaching them to the tube, (3) forming a band and which is then surrounded around the tube, (4) extrusion of the fins directly on the tube by means of a screw-shaped mold.

La technique (1) requiert la formation d'un moule spécial pour les ailettes, les techniques (2) à (4) requièrent un post-traitement de réticulation des ailettes. Pour les applications extérieures, toutes les techniques (1) à (4) utilisent généralement des matériaux à base de silicone du fait de leur hydrophobicité.The technique (1) requires the formation of a special mold for the fins, the techniques (2) to (4) require a post-treatment of cross-linking of the fins. For exterior applications, all techniques (1) to (4) generally use silicone-based materials because of their hydrophobicity.

Dans l'ensemble de la présente description, on entend par « silicone » ou par « caoutchouc silicone » un matériau élastomère composite composé de résine polymérique silicone, mono-composant ou bi-composant, éventuellement renforcée par une charge minérale.Throughout the present description, the term "silicone" or "silicone rubber" a composite elastomeric material composed of silicone polymer resin, single-component or two-component, optionally reinforced with a mineral filler.

Par exemple, le document EP-A-1091365 [1] décrit un isolateur constitué d'un tube en résine époxyde renforcé par des fibres et entouré d'une protection isolante constituée de caoutchouc silicone. Cette protection peut être sous la forme d'ailettes. L'isolateur peut être obtenu par moulage du caoutchouc silicone vulcanisé sur le tube en résine époxyde renforcé par des fibres. On utilise le silicone pour ses propriétés d'hydrophobicité et de transfert d'hydrophobicité.For example, the document EP-A-1091365 [1] discloses an insulator made of a fiber reinforced epoxy tube and surrounded by an insulating protection made of silicone rubber. This protection may be in the form of fins. The insulator can be obtained by molding the vulcanized silicone rubber on the fiber reinforced epoxy tube. Silicone is used for its hydrophobicity and hydrophobicity transfer properties.

Ces isolateurs comportent cependant une interface de deux matériaux différents entre le tube et les ailettes, ce qui peut entraîner des vides et des phénomènes de délaminations du fait des coefficients de dilatations thermiques différents, et conduit, lors de l'utilisation de ces isolateurs à des décharges partielles et par la suite à des claquages.These insulators, however, have an interface of two different materials between the tube and the fins, which can cause voids and delamination phenomena due to different coefficients of thermal expansion, and leads, when using these insulators to partial discharges and subsequently to breakdowns.

Seule l'utilisation d'un primaire d'adhésion permet de renforcer l'adhésion à l'interface du matériau du tube creux et du matériau constituant les ailettes. Les coûts de matériaux et de fabrication sont élevés. Le caoutchouc silicone utilisé est un matériau onéreux. Ces procédés sont complexes et comprennent un nombre important d'étapes de fabrication pour obtenir un isolateur.Only the use of an adhesion primer strengthens the adhesion to the interface of the material of the hollow tube and the material constituting the fins. Material and manufacturing costs are high. The silicone rubber used is an expensive material. These methods are complex and include a large number of manufacturing steps to obtain an insulator.

Le document WO 02/061767 [2] décrit une coque (« housing ») pour un appareil électrique. Cette coque comprend un tube appelé gaine (« sheath »), au moins une ailette, et un revêtement hydrophobe disposé sur l'ailette. Le tube est constitué de silicone à haute température de vulcanisation (type « HTV » pour « High Temperature Vulcanising »), l'ailette de silicone est constituée d'un silicone à température ambiante de vulcanisation (type « RTV » pour « Room Temperature Vulcanising ») et le revêtement hydrophobe de caoutchouc silicone liquide (« LS rubber ») et de silicone RTV. Le silicone liquide est travaillé par moulage, et le silicone solide par extrusion.The document WO 02/061767 [2] describes a housing for an electrical appliance. This shell comprises a tube called sheath, at least one fin, and a hydrophobic coating disposed on the fin. The tube is made of high temperature silicone vulcanization (type "HTV" for "High Temperature Vulcanising "), the silicone fin consists of room temperature vulcanizing silicone (" RTV "type) and the hydrophobic coating of liquid silicone rubber (" LS rubber ") and silicone RTV. Liquid silicone is molded, and solid silicone is extruded.

Pour cet isolateur également, les matériaux utilisés sont coûteux et le procédé de fabrication est compliqué.For this insulator also, the materials used are expensive and the manufacturing process is complicated.

Ainsi, les fabricants d'isolateurs de l'art antérieur préconisent l'utilisation de matériaux différents pour le tube et la gaine, du fait de leur fonction et de leur sollicitation différentes lors de l'utilisation de l'isolateur. En outre, aujourd'hui, le silicone est le matériau utilisé de façon préférentielle et habituelle pour réaliser ce type d'isolateur.Thus, the manufacturers of prior art insulators recommend the use of different materials for the tube and the sheath, due to their different function and stress when using the insulator. In addition, today, silicone is the material used preferentially and usual for producing this type of insulator.

De nombreux inconvénients liés à l'utilisation du silicone peuvent être cités. L'inconvénient majeur est la modification des propriétés mécaniques du silicone lorsqu'il est soumis aux agents atmosphériques et au rayonnement UV (vieillissement climatique). En effet ce matériau devient fragile et des ailettes peuvent se fissurer ou même se rompre en service. De même la fragilité du matériau rend très difficile les opérations de maintenance sur site : toute fausse manoeuvre peut conduire à l'endommagement des ailettes et donc de l'isolateur.Many disadvantages related to the use of silicone can be cited. The major disadvantage is the modification of the mechanical properties of the silicone when it is subjected to the atmospheric agents and the UV radiation (climatic aging). Indeed this material becomes fragile and fins may crack or even break in service. Similarly, the fragility of the material makes it very difficult to perform maintenance operations on site: any false maneuver can lead to damage to the fins and thus to the insulator.

La manutention de ces isolateurs à ailettes en silicone est particulièrement délicate. En effet, les ailettes peuvent être facilement endommagées lors de la réception en usine des isolateurs lors de la découpe au cutter de l'emballage : il est fréquent de retrouver des isolateurs avec des ailettes coupées ou lacérées.The handling of these insulators with silicone fins is particularly delicate. Indeed, fins can be easily damaged when receiving insulators at the factory when cutting the cutter packaging: it is common to find insulators with cut or lacerated fins.

Les problèmes typiques de manutention ou de tenue dans le temps des isolateurs composites sont particulièrement bien traités dans la brochure thématique CIGRE N°184 d'avril 2001 « Composite Insulator Handling Guide » ou dans la publication suivante : « IEEE Task Force Report : Brittle Fracture in Nonceramic Insulators », IEEE Transactions on Power Delivery, Vol 17, N°3, July 2002, pp 848-856 [3].Typical problems with handling or withstanding the time of composite insulators are particularly well handled in the CIGRE thematic brochure N ° 184 of April 2001 "Composite Insulator Handling Guide" or in the following publication: "IEEE Task Force Report: Brittle Fracture in Nonceramic Insulators," IEEE Transactions on Power Delivery, Vol 17, No. 3, July 2002, pp 848-856 [3].

Tout défaut des ailettes sera un point de faiblesse pour la tenue dans le temps de l'isolateur. De même, des ailettes peuvent être déchirées lorsque l'isolateur est posé en appui sur une partie anguleuse.Any defect of the fins will be a point of weakness for the holding in time of the insulator. Similarly, fins may be torn when the insulator is resting on an angled portion.

Par ailleurs, en utilisation, il a été constaté que le silicone peut être attaqué par des animaux, tels que des oiseaux ou des rongeurs.Furthermore, in use, it has been found that the silicone can be attacked by animals, such as birds or rodents.

Le document « Hydrophobic cycloaliphatic epoxy : Latest findings and future developments », Christian Beisele, 2001 World Insulator Congress and Exhibition, 18-21 November, Shangai., CHINA [4] décrit pour la première fois le remplacement du silicone par une résine époxyde cycloaliphatique pour la fabrication de composants isolants, en particulier d'isolateurs à tube plein. La résine époxyde est présentée comme étant un matériau isolant alternatif intéressant et moins onéreux. L'isolateur est fabriqué par un procédé de gélation sous pression. Le procédé n'est pas détaillé.The document "Hydrophobic cycloaliphatic epoxy: Latest findings and future developments", Christian Beisele, 2001 World Insulator Congress and Exhibition, 18-21 November, Shanghai, CHINA [4] describes for the first time the replacement of silicone with a cycloaliphatic epoxy resin for the manufacture of insulating components, in particular solid-tube insulators. The epoxy resin is presented as an interesting and less expensive alternative insulating material. The insulator is manufactured by a pressure freezing process. The process is not detailed.

Les résines utilisées dans ce document ne permettent pas de pallier à l'ensemble des inconvénients décrits ci-dessus : elles ne résistent pas bien aux agressions externes en opération (rongeurs, oiseaux, pluie, pollution, etc.), au cheminement et à l'érosion (résine de classe 1B3, 5 selon la norme CEI 60587). En outre, elles ne résistent pas bien aux manipulations en usine, au montage sur site, se coupent ou se déchirent lors de l'ouverture des emballages. En effet ces matériaux ont des caractéristiques mécaniques semblables au silicone. Ainsi, on peut s'attendre aux mêmes problèmes au cours du procédé de fabrication de l'isolateur, en montage pour son utilisation comme isolateur et en opération.The resins used in this document do not make it possible to overcome all of the disadvantages described above: they do not withstand external aggression in operation (rodents, birds, rain, pollution, etc.), tracking, and the like. erosion (class 1B3 resin, according to IEC 60587). In addition, they do not withstand handling in the factory, mounting on site, cut or tear when opening packages. Indeed, these materials have mechanical characteristics similar to silicone. Thus, the same problems can be expected during the manufacturing process of the insulator, in assembly for its use as an insulator and in operation.

Le document GB-A-2 147 225 décrit un isolateur électrique dans lequel le matériau isolant comprend une résine qui n'est pas une résine flexibilisée mais bien plutôt une résine rigide, cassante.The document GB-A-2,147,225 discloses an electrical insulator in which the insulating material comprises a resin which is not a flexibilized resin but rather a rigid, brittle resin.

Le document US-A-3,645,899 a trait à un isolateur électrique constitué d'une masse monolithique d'un matériau isolant comprenant une résine époxyde chargée, durcie. Dans cet isolateur, l'isolant est donc sous la forme d'un bloc et non d'une gaine.The document US Patent 3,645,899 relates to an electrical insulator consisting of a monolithic mass of an insulating material comprising a charged, cured epoxy resin. In this insulator, the insulation is in the form of a block and not a sheath.

Aucun des documents susnommés ne propose de solution à l'ensemble des inconvénients précités.None of the aforementioned documents offers a solution to all the aforementioned drawbacks.

Il existe donc un réel besoin d'un isolateur moins onéreux que ceux de l'art antérieur, tant en termes de matériaux utilisés pour sa fabrication que de mise en oeuvre de son procédé de fabrication, ayant un comportement au vieillissement amélioré, notamment en renforçant ou en supprimant l'interface entre le matériau du tube et le matériau constituant la gaine, et en utilisant un ou des matériaux qui répondent aux inconvénients précités et remplissent leur rôle isolant dans l'isolateur obtenu.There is therefore a real need for a less expensive insulator than those of the prior art, both in terms of materials used for its manufacture and implementation of its manufacturing process, having an improved aging behavior, in particular by reinforcing or by removing the interface between the tube material and the material constituting the sheath, and using one or more materials that meet the aforementioned drawbacks and fulfill their insulating role in the insulator obtained.

Exposé de l'inventionPresentation of the invention

La présente invention se rapporte précisément à un isolateur électrique qui répond à ce besoin et à d'autres encore. L'isolateur électrique de la présente invention est défini dans la revendication 1. Il comprend un tube creux ou plein entouré d'une gaine isolante. La gaine isolante peut être lisse ou munie d'ailettes.The present invention specifically relates to an electrical insulator that meets this and other needs. The electrical insulator of the present invention is defined in claim 1. It comprises a hollow or solid tube surrounded by a insulating sheath. The insulating sheath may be smooth or finned.

L'isolateur de la présente invention est caractérisée en ce que la gaine isolante est constituée d'une résine époxyde cycloaliphatique hydrophobe flexibilisée chargée durcie obtenue par durcissement d'un mélange comprenant : de 25 à 75 % en poids de charge minérale, de préférence de 30 à 70 % en poids de charge minérale, de préférence de 40 à 60 % en poids de charge minérale, de préférence encore de 45 à 55 % en poids de charge minérale, par exemple 50 % en poids, une résine époxyde cycloaliphatique hydrophobe et un durcisseur.The insulator of the present invention is characterized in that the insulating sheath is made of a hardened charged flexibilized hydrophobic cycloaliphatic epoxy resin obtained by curing a mixture comprising: from 25 to 75% by weight of mineral filler, preferably 30 to 70% by weight of mineral filler, preferably 40 to 60% by weight of inorganic filler, more preferably 45 to 55% by weight of inorganic filler, for example 50% by weight, a hydrophobic cycloaliphatic epoxy resin and a hardener.

Ici, les pourcentages en poids sont indiqués par rapport à la masse totale de la résine chargée, c'est à dire résine + durcisseur + charge.Here, the percentages by weight are indicated with respect to the total mass of the charged resin, ie resin + hardener + charge.

Dans la suite de la présente description, on entend par « résine chargée » un matériau composite composé d'une résine époxyde, d'un durcisseur et d'une charge minérale. Le rôle de la charge minérale est d'améliorer les propriétés mécaniques de la résine durcie ainsi que sa tenue à l'érosion et au cheminement électrique.In the remainder of the present description, "charged resin" is understood to mean a composite material composed of an epoxy resin, a hardener and a mineral filler. The role of the mineral filler is to improve the mechanical properties of the hardened resin as well as its resistance to erosion and electrical flow.

La résine chargée durcie de la présente invention est une résine dite « flexibilisée ». Ainsi, cette résine une fois polymérisée présente des propriétés mécaniques particulières telles qu'un module d'élasticité et une déformation à la rupture très élevés, à savoir un module d'élasticité allant de 200 à 4000 MPa et une déformation à la rupture allant de 10 à 30%. Cette résine chargée durcie est généralement obtenue par mélange de résine de base pouvant être spécialement formulée permettant d'obtenir, en fin de processus de durcissement une résine durcie flexibilisée, de durcisseur(s) spécialement formulé(s) dans le but d'obtenir une résine durcie flexibilisée et de possibles additifs tels que des flexibilisateurs (ces deux voire trois éléments réagissant chimiquement ensemble, permettant d'obtenir une résine durcie flexibilisée), ainsi que des charges minérales.The cured filled resin of the present invention is a so-called "flexibilized" resin. Thus, this resin, once polymerized, has particular mechanical properties such as a very high modulus of elasticity and deformation at break, namely a modulus of elasticity ranging from 200 to 4000 MPa and a deformation at break ranging from 10 to 30%. This hardened filled resin is generally obtained by mixing a specially formulated base resin to obtain, at the end of the hardening process, a flexibilised hardened resin, hardener (s) specially formulated for the purpose of obtaining a flexibilised hardened resin and possible additives such as flexibilizers (these two or even three elements chemically reacting together, to obtain a flexibilized hardened resin), as well as mineral fillers.

Les termes « résine flexibilisée » sont des termes couramment utilisés dans ce domaine de la technique et dont la signification est parfaitement claire et sans ambiguïté pour l'homme du métier. La flexibilisation des résines peut être obtenue par modification chimique des molécules de durcisseur et potentiellement de résine, et/ou potentiellement par incorporation de flexibilisateur (chaînes flexibles telles que des chaînes aliphatiques) lors de la polymérisation.The term "flexibilized resin" is a term commonly used in this field of the art and whose meaning is perfectly clear and unambiguous to those skilled in the art. Flexibility of the resins can be achieved by chemically modifying the hardener and potentially resin molecules, and / or potentially incorporating flexibilizer (flexible chains such as aliphatic chains) upon polymerization.

Une résine flexibilisée peut avoir un taux de réticulation réduit par rapport à cette résine avant tout traitement de flexibilisation.A flexibilized resin may have a reduced degree of crosslinking with respect to this resin prior to any flexibilization treatment.

Généralement la flexibilisation d'une résine durcie est obtenue principalement par modification du durcisseur cycloaliphatique en éloignant les deux cycles aliphatiques réactifs par insertion d'une chaîne aliphatique.Generally, the flexibilization of a cured resin is obtained mainly by modifying the cycloaliphatic hardener by removing the two reactive aliphatic rings by insertion of an aliphatic chain.

La résine époxyde cycloaliphatique flexibilisée chargée durcie de la présente invention, présente un module d'élasticité de 200 à 4000 MPa.The cured loaded flexibilized cycloaliphatic epoxy resin of the present invention has a modulus of elasticity of 200 to 4000 MPa.

La résine époxyde cycloaliphatique hydrophobe flexibilisée chargée durcie utilisée dans la présente invention a une température de transition vitreuse de 0 à 50°C, de préférence de 10 à 30°C, de préférence encore de 18 à 30°C, un module d'élasticité de 200 à 4000 MPa ; une élongation à la rupture de 10 à 30 % ; une contrainte à la rupture de 14 à 40 MPa : et en outre une dureté shore A supérieure à 98, et/ou une résistance au cheminement et à l'érosion de classe supérieure ou égale à 1A3,5 ou 1B3,5 selon la norme CEI 60587.The cured loaded flexibilized hydrophobic cycloaliphatic epoxy resin used in the present invention has a glass transition temperature of 0 to 50 ° C, preferably 10 to 30 ° C, more preferably 18 to 30 ° C, a modulus of elasticity from 200 to 4000 MPa; an elongation at break of 10 to 30%; a breaking stress of 14 to 40 MPa: and in addition a shore A hardness greater than 98, and / or a resistance to tracking and erosion of class 1A3.5 or 1B3.5 or higher according to the standard IEC 60587.

La solution apportée par la présente invention aux nombreux inconvénients précités consiste en l'utilisation de cette résine cycloaliphatique hydrophobe flexibilisée chargée durcie dont les caractéristiques mécaniques sont comparées aux matériaux de l'art antérieur dans le tableau I ci-dessous. Tableau I Document [4] Résine époxyde non flexibilisée chargée durcie (valeurs typiques) Silicone (valeurs typiques) Résine époxyde cycloaliphatique hydrophobe flexibilisée durcie chargée de la présente invention LMB5727 / 5728 LMB5729 / 5730 Dureté shore A 89 . 97 >95 30-80 >98 Contrainte à la rupture (MPa) 3 6 >60 5-8 15-40 Elongation à la rupture (%) 60 65 ~1 >100 10-30 Module d'élasticité (Mpa) 24 53 >10000 <50 200-4000 Résistance au cheminement et à l'érosion 1B3,5 1B3,5 >1B3,5 1B4,5 -1B4,5 The solution provided by the present invention to the aforementioned numerous drawbacks consists in the use of this hardened loaded flexibilized hydrophobic cycloaliphatic resin whose mechanical characteristics are compared with the materials of the prior art in Table I below. Table I Document [4] Hardened non-flexibilized epoxy resin hardened (typical values) Silicone (typical values) Hardened flexibilized hydrophobic cycloaliphatic epoxy resin charged with the present invention LMB5727 / 5728 LMB5729 / 5730 Shore A hardness 89. 97 > 95 30-80 > 98 Stress at break (MPa) 3 6 > 60 5-8 15-40 Elongation at break (%) 60 65 1 ~ > 100 10-30 Modulus of elasticity (Mpa) 24 53 > 10000 <50 200-4000 Resistance to tracking and erosion 1B3,5 1B3,5 > 1B3,5 1B4,5 -1B4,5

Selon l'invention, la charge minérale comprend de préférence de 25 à 75% en poids de trihydrate d'alumine (ATH) (Al(OH)3), de préférence 40 à 60% en poids, par exemple 50% en poids, le reste étant constitué d'au moins un autre matériau de charge minérale.According to the invention, the inorganic filler preferably comprises 25 to 75% by weight of alumina trihydrate (ATH) (Al (OH) 3 ), preferably 40 to 60% by weight, for example 50% by weight, the remainder being at least one other mineral filler material.

Selon l'invention, l'autre matériau de charge minérale peut être choisi avantageusement dans le groupe comprenant l'alumine (Al2O3), la silice (SiO2), l'oxyde de calcium (CaO), l'oxyde de magnésium (MgO), l'oxyde de Zinc (ZnO), le fluorure de silicium, la wollastonite, le carbonate de calcium (CaCO3), l'oxyde de titane (TiO2), des nanoparticules d'argile ou un mélange de deux ou plus de ceux-ci.According to the invention, the other inorganic filler material may advantageously be chosen from the group comprising alumina (Al 2 O 3 ), silica (SiO 2 ), calcium oxide (CaO), magnesium (MgO), zinc oxide (ZnO), silicon fluoride, wollastonite, calcium carbonate (CaCO 3 ), oxide titanium (TiO 2 ), clay nanoparticles or a mixture of two or more thereof.

De préférence, l'autre matériau de charge est de l'alumine ou de la silice ou un mélange d'alumine et de silice. Ainsi, dans ce cas, la charge minérale comprend de 25 à 75% en poids de trihydrate d'alumine, de préférence de 40 à 60% en poids de trihydrate d'alumine, par exemple 50% en poids, le reste étant constitué d'alumine ou de silice ou d'un mélange d'alumine et de silice. Lorsqu'on utilise un mélange d'alumine et de silice, ce mélange peut être constitué par exemple de 1 à 99% en poids d'alumine, par exemple de 5 à 95% en poids d'alumine, par exemple de 30 à 70% en poids d'alumine, le reste étant de la silice.Preferably, the other filler material is alumina or silica or a mixture of alumina and silica. Thus, in this case, the inorganic filler comprises from 25 to 75% by weight of alumina trihydrate, preferably from 40 to 60% by weight of alumina trihydrate, for example 50% by weight, the remainder consisting of alumina or silica or a mixture of alumina and silica. When a mixture of alumina and silica is used, this mixture may consist, for example, of from 1 to 99% by weight of alumina, for example from 5 to 95% by weight of alumina, for example from 30 to 70% by weight. % by weight of alumina, the remainder being silica.

Selon l'invention, la charge minérale est de préférence composée de particules de différentes granulométries : des particules d'un ou de plusieurs types chimiques parmi ceux cités ci-dessus (charge minérale) de taille submicronique et des particules d'un ou de plusieurs types chimiques parmi ceux cités ci-dessus (charge minérale) de taille micronique, ces particules de renfort de tailles distinctes pouvant être de composition chimique identique ou différente. Ainsi, selon l'invention, la charge minérale peut être un mélange de charge de taille micronique et de taille submicronique. En outre, selon l'invention, les particules de taille micronique peuvent être de plusieurs compositions chimiques différentes, de même que les particules de taille submicronique.According to the invention, the mineral filler is preferably composed of particles of different particle sizes: particles of one or more of the chemical types mentioned above (mineral filler) of submicron size and particles of one or more chemical types among those mentioned above (mineral filler) of micron size, these reinforcing particles of different sizes may be of identical or different chemical composition. Thus, according to the invention, the inorganic filler may be a mixture of micron-size filler and submicron size. In addition, according to the invention, the micron-size particles may be of several different chemical compositions, as well as the submicron-sized particles.

Avantageusement, les particules de taille submicronique ont une taille au minimum deux fois plus petite que la taille des particules de taille micronique.Advantageously, the particles of submicron size have a size at least twice as much small as the size of micron sized particles.

Notons que la notion de taille se rapporte au « diamètre médian » de la distribution des particules dans le cas où les particules utilisées ont une géométrie proche de la géométrie sphérique. On rappelle que le « diamètre médian » est le diamètre de la particule au niveau de la médiane de la distribution des diamètres des particules, la médiane représentant la valeur où la fréquence totale des valeurs au-dessus et la fréquence totale au-dessous de cette valeur sont identiques. Dans le cas où les particules utilisées présentent des morphologies avec de forts facteurs de forme, comme par exemple des morphologies lamellaires telles que des feuillets ou des bâtonnets, la notion de taille se rapporte alors à la plus grande dimension de la particule, par exemple la longueur dans le cas d'un feuillet.Note that the notion of size refers to the "median diameter" of the particle distribution in the case where the particles used have a geometry close to the spherical geometry. It is recalled that the "median diameter" is the diameter of the particle at the median of the particle diameter distribution, the median representing the value where the total frequency of the values above and the total frequency below that value. value are identical. In the case where the particles used have morphologies with strong form factors, for example lamellar morphologies such as leaflets or rods, the notion of size then relates to the largest dimension of the particle, for example the length in the case of a leaflet.

Notons que la taille des particules de taille submicronique est inférieure ou égal à un micromètre, et que la taille des particules de taille micronique est supérieure à un micromètre.It should be noted that the size of the particles of submicron size is less than or equal to one micrometer, and that the size of the micron-sized particles is greater than one micrometer.

Selon l'invention, avantageusement, les particules de taille micronique ont une taille comprise entre 1 et 30 micromètres et les particules de taille submicronique ont une taille inférieure à 1 micromètre.According to the invention, advantageously, the micron-sized particles have a size of between 1 and 30 microns and the particles of submicron size have a size of less than 1 micrometer.

Selon l'invention, avantageusement, les particules de taille submicronique ont une taille de quelques centaines de nanomètres et au minimum de 5 nanomètres.According to the invention, advantageously, the particles of submicron size have a size of a few hundred nanometers and a minimum of 5 nanometers.

De préférence les particules de la ou des charge(s) minérale(s) sont traitées chimiquement en surface afin d'améliorer le mouillage et l'adhérence avec la résine époxyde. De préférence, la silice est modifiée par silanisation.Preferably the particles of the mineral filler (s) are surface-chemically treated to improve wetting and adhesion with the epoxy resin. Preferably, the silica is modified by silanization.

Selon l'invention, le mélange permettant après durcissement l'obtention d'une résine époxyde cycloaliphatique hydrophobe flexibilisée chargée durcie comprend une résine époxyde de base de type cycloaliphatique hydrophobe non modifiée.According to the invention, the mixture which, after curing, makes it possible to obtain a hardened charged flexibilized hydrophobic cycloaliphatic epoxy resin comprises an unmodified hydrophobic cycloaliphatic base epoxy resin.

Selon l'invention, ledit mélange comprend également un durcisseur. L'un quelconque des durcisseurs de résine époxyde cycloaliphatique connus de l'homme du métier peut être utilisé pour mettre en oeuvre la présente invention. Il peut s'agir par exemple d'un anhydride cycloaliphatique. La quantité de ce durcisseur est en générale de 60 à 100% en poids par rapport à la masse totale de la résine non chargée utilisée dans la présente invention.According to the invention, said mixture also comprises a hardener. Any of the cycloaliphatic epoxy resin hardeners known to those skilled in the art can be used to practice the present invention. It may be for example a cycloaliphatic anhydride. The amount of this hardener is generally 60 to 100% by weight based on the total mass of the unloaded resin used in the present invention.

Comme on l'a mentionné plus haut, le durcisseur peut être chimiquement modifié pour flexibiliser la résine une fois durcie. Ce composant étant connu sous le nom de durcisseur flexibilisateur.As mentioned above, the hardener can be chemically modified to flexibilize the resin once cured. This component is known as a flexibilizer hardener.

Selon l'invention, ledit mélange peut comprendre des additifs chimiques dont des flexibilisants, accélérateurs, un ou plusieurs additifs spécifiques permettant de rendre la résine hydrophobe choisis parmi un polysiloxane à terminaisons -OH, un copolymère polysiloxane/polyéther et un polysiloxane cyclique ou un mélange de deux ou trois de ces polysiloxanesAccording to the invention, said mixture may comprise chemical additives including flexibilizers, accelerators, one or more specific additives making it possible to make the resin hydrophobic chosen from an -OH-terminated polysiloxane, a polysiloxane / polyether copolymer and a polysiloxane cyclic or a mixture of two or three of these polysiloxanes

Selon l'invention, ledit mélange peut comprendre en outre des sphères élastomères. Dans ce cas, elles sont ajoutées à raison de 5 à 10% en poids de sphères élastomères. Ce pourcentage est bien entendu exprimé par rapport au poids de la résine époxyde cycloaliphatique hydrophobe chargée. Ces sphères permettent d'absorber l'énergie des chocs que peut subir l'isolateur. Il peut s'agir par exemple de sphères Durastrength Impact Modifier (marque de commerce) commercialisées par la société Arkema.According to the invention, said mixture may further comprise elastomeric spheres. In this case, they are added at a rate of 5 to 10% by weight of elastomeric spheres. This percentage is of course expressed relative to the weight of the hydrophobic cycloaliphatic epoxy resin loaded. These spheres absorb the energy of shocks that may suffer the insulator. These may be, for example, Durastrength Impact Modifier spheres (trademark) marketed by Arkema.

Selon l'invention, ledit mélange peut comprendre en outre un ou plusieurs additif(s), choisi(s) parmi un polysiloxane à terminaisons -OH, un copolymère polysiloxane/polyéther et un polysiloxane cyclique ou un mélange de deux ou trois de ces polysiloxanes. Plus précisément, il peut s'agir par exemple de dodécamethylcyclohexasiloxane. La quantité de ce ou ces additif(s) est en générale de 1 à 10% en poids par rapport à la masse totale de la résine chargée utilisée dans la présente invention.According to the invention, said mixture may further comprise one or more additive (s) chosen from an -OH-terminated polysiloxane, a polysiloxane / polyether copolymer and a cyclic polysiloxane or a mixture of two or three of these polysiloxanes. . More specifically, it may be for example dodecamethylcyclohexasiloxane. The amount of this or these additive (s) is generally from 1 to 10% by weight relative to the total mass of the filled resin used in the present invention.

Selon l'invention, la charge minérale est de préférence desséchée et dégazée avant d'être mélangée à la résigne époxyde pour former la résine époxyde cycloaliphatique hydrophobe utilisée dans la présente invention. En effet, cela permet d'améliorer la dispersion de la charge dans la résine et d'obtenir un mélange homogène. Ce séchage et dégazage peuvent être effectués simultanément, par exemple en plaçant la charge minérale sous vide à une température de 70 à 100°C, par exemple pendant 10 à 30 heures.According to the invention, the inorganic filler is preferably desiccated and degassed before being mixed with the epoxy resin to form the hydrophobic cycloaliphatic epoxy resin used in the present invention. Indeed, this makes it possible to improve the dispersion of the filler in the resin and to obtain a homogeneous mixture. This drying and degassing can be carried out simultaneously, for example by placing the mineral filler under vacuum at a temperature of 70 to 100 ° C, for example for 10 to 30 hours.

La résine époxyde cycloaliphatique hydrophobe flexibilisée chargée durcie utilisée dans la présente invention peut être préparée par simple mélange de la résine non durcie, de la charge et du durcisseur et des additifs éventuels. De préférence, ce mélange est bien entendu réalisé de façon à obtenir un mélange homogène, c'est-à-dire une dispersion homogène de la charge minérale et du durcisseur et des additifs éventuels dans la résine.The cured loaded flexibilized hydrophobic cycloaliphatic epoxy resin used in the present invention can be prepared by simply mixing the uncured resin, the filler and the hardener and any additives. Preferably, this mixture is of course designed so as to obtain a homogeneous mixture, that is to say a homogeneous dispersion of the mineral filler and hardener and any additives in the resin.

Avantageusement, une partie de la charge minérale, de préférence séchée et dégazée, est mélangée à la résine liquide (c'est-à-dire non durcie), une autre partie de la charge minérale, de préférence séchée et dégazée, est mélangée au durcisseur liquide, et les deux mélanges obtenus sont mélangés ensemble pour former une résine chargée utilisable dans la présente invention. Cette mise en oeuvre permet une bonne homogénéisation. De préférence, chaque mélange est réalisé à une température de 40 à 60°C et dégazé. Les mélanges peuvent être réalisés mécaniquement, par exemple sous forme de malaxage.Advantageously, a part of the inorganic filler, preferably dried and degassed, is mixed with the liquid resin (that is to say uncured resin), another part of the mineral filler, preferably dried and degassed, is mixed with liquid hardener, and the two mixtures obtained are mixed together to form a filled resin for use in the present invention. This implementation allows good homogenization. Preferably, each mixture is made at a temperature of 40 to 60 ° C and degassed. The mixtures can be made mechanically, for example in the form of kneading.

L'isolateur de la présente invention comprend également un tube. Selon l'invention, le tube de l'isolateur peut être un tube plein ou creux. Il permet de conférer à l'isolateur sa tenue mécanique. Il peut être flexible ou rigide. De préférence, il est rigide.The insulator of the present invention also includes a tube. According to the invention, the insulator tube may be a solid or hollow tube. It gives the insulator its mechanical strength. It can be flexible or rigid. Preferably, it is rigid.

Selon l'invention, qu'il soit plein ou creux, la géométrie du tube n'est pas limitée à une forme particulière. Elle est choisie notamment en fonction de l'application envisagée. Il peut s'agir par exemple d'un tube choisi parmi un tube droit, un tube conique, un tube tronconique, un tube en forme de tonneau, etc. ou d'un tube présentant une combinaison de ces différentes formes ou géométries. Le plus souvent, le tube est droit, ou de forme conique ou tronconique ou en forme de tonneau.According to the invention, whether solid or hollow, the geometry of the tube is not limited to a particular shape. It is chosen in particular according to the intended application. It may be for example a tube chosen from a straight tube, a conical tube, a frustoconical tube, a barrel-shaped tube, etc. or a tube having a combination of these different shapes or geometries. Most often, the tube is straight, or conical or frustoconical or barrel-shaped.

Selon l'invention, la section du tube n'est pas non plus limitée à une géométrie particulière. Elle est choisie notamment en fonction de l'application envisagée. Elle est le plus couramment ronde, mais elle peut également être carrée, triangulaire, polygonale, par exemple de 5 à 30 côtés. La facilité de sa fabrication peut aussi être un critère pour choisir la géométrie du tube et de sa section.According to the invention, the section of the tube is also not limited to a particular geometry. It is chosen in particular according to the intended application. It is most commonly round, but it can also be square, triangular, polygonal, for example from 5 to 30 sides. The ease of its manufacture can also be a criterion for choosing the geometry of the tube and its section.

Selon l'invention, le tube (plein ou creux) peut être par exemple un tube en résine polymérique thermodurcissable ou thermoplastique renforcée de fibres courtes ou longues de nature chimique minérale ou organique. On entend par fibres courtes des fibres de longueur moyenne inférieure à 30 mm. On entend par fibres longues, des fibres de longueur moyenne supérieure à 30 mm. Dans le cas de réalisation d'un tube composé d'une résine thermodurcissable ou thermoplastique renforcée par des fibres courtes, le tube est réalisé par injection. Les points d'injections sont définis de manière à obtenir un bon alignement des fibres parallèlement à l'axe du tube.According to the invention, the tube (solid or hollow) may for example be a thermosetting polymer or thermoplastic resin tube reinforced with short or long fibers of mineral or organic chemical nature. Short fibers are fibers of average length less than 30 mm. By long fibers are meant fibers of average length greater than 30 mm. In the case of producing a tube made of a thermosetting or thermoplastic resin reinforced with short fibers, the tube is made by injection. The injection points are defined so as to obtain a good alignment of the fibers parallel to the axis of the tube.

Selon l'invention, que le tube soit plein ou creux, il peut être avantageusement constitué à partir d'un arrangement de fibres en forme de tube. Ces fibres peuvent être longues ou courtes. L'arrangement de fibres peut être formé par exemple par enroulement filamentaire de fibres longues ou à partir de fibres courtes.According to the invention, whether the tube is solid or hollow, it may advantageously be formed from a tube-shaped fiber arrangement. These fibers can be long or short. The fiber arrangement can be formed for example by filament winding of long fibers or from short fibers.

Dans le cas de l'utilisation d'un arrangement de fibres, celui-ci peut être constitué par exemple d'un arrangement de fibres choisi parmi un mat de fibres ou un tissu de fibres unidimensionnelles, bidimensionnelles ou tridimensionnelles. L'arrangement de fibres peut être sous forme tissé ou non tissé.In the case of the use of a fiber arrangement, it may consist for example of a fiber arrangement selected from a fiber mat or a fabric of one-dimensional, two-dimensional or three-dimensional fibers. The fiber arrangement may be in woven or nonwoven form.

Quel que soit l'arrangement de fibres choisi, selon l'invention, les fibres sont de préférence choisies parmi des fibres minérales telles que les fibres de verre, des fibres de quartz, des fibres de carbure de silicium, ou parmi des fibres organiques telles que les fibres d'aramide, par exemple de kevlar (marque de commerce), des fibres de polyester, et des fibres de polybenzobisoxazole, par exemple de zylon (marque de commerce).Whatever the fiber arrangement chosen, according to the invention, the fibers are preferably chosen from mineral fibers such as glass fibers, quartz fibers, silicon carbide fibers, or from organic fibers such as aramid fibers, e.g. kevlar (trade mark), polyester fibers, and polybenzobisoxazole fibers, e.g. zylon (trademark).

Selon l'invention, les fibres de l'arrangement sont de préférence imprégnées par une résine époxyde, et de préférence encore par une résine époxyde cycloaliphatique, par exemple d'une résine époxyde cycloaliphatique hydrophobe chargée par un renfort particulaire organique ou inorganique (tel que l'alumine, la silice ou un mélange des deux) conforme à la présente invention, telle que définie ci-dessus. Par exemple, l'arrangement de fibres est imprégné de résine époxyde cycloaliphatique hydrophobe comprenant de 25 à 75% en poids de charge minérale et un durcisseur.According to the invention, the fibers of the arrangement are preferably impregnated with an epoxy resin, and more preferably with a cycloaliphatic epoxy resin, for example a hydrophobic cycloaliphatic epoxy resin loaded with an organic or inorganic particulate reinforcement (such as alumina, silica or a mixture of both) according to the present invention, as defined above. For example, the fiber arrangement is impregnated with hydrophobic cycloaliphatic epoxy resin comprising from 25 to 75% by weight mineral filler and a hardener.

Les fibres, plus particulièrement les fibres minérales, peuvent présenter / être soumises à un traitement de surface spécifique afin d'améliorer leur compatibilité avec la résine d'imprégnation, notamment la mouillabilité de la résine sur les fibres. L'arrangement de fibres constitue donc un précurseur du tube de l'isolateur de la présente invention.The fibers, more particularly the mineral fibers, may have / be subjected to a specific surface treatment in order to improve their compatibility with the impregnating resin, in particular the wettability of the resin on the fibers. The fiber arrangement thus constitutes a precursor of the insulator tube of the present invention.

Selon l'invention, le tube (plein ou creux) peut être par exemple un tube en résine polymérique thermodurcissable ou thermoplastique renforcée de charge inorganique ou organique, par exemple un tube en résine époxyde renforcée par de l'alumine ou de la silice.According to the invention, the tube (solid or hollow) may be for example a thermosetting or thermoplastic polymeric resin tube reinforced with inorganic or organic filler, for example an epoxy resin tube reinforced with alumina or silica.

La présente invention se rapporte de manière générale à l'utilisation, telle que définie dans la revendication 29, d'une résine époxyde cycloaliphatique hydrophobe flexibilisée chargée durcie obtenue par durcissement d'un mélange comprenant de 25 à 75% en poids de charge minérale, de préférence de 30 à 70% en poids de charge minérale, de préférence de 40 à 60% en poids de charge minérale, de préférence encore de 45 à 55% en poids de charge minérale, par exemple 50% en poids, une résine époxyde cycloaliphatique hydrophobe et un durcisseur pour la fabrication d'un isolateur électrique, en particulier pour la fabrication de la gaine extérieure d'un isolateur, cette gaine pouvant être munie d'ailettes ou non. La résine époxyde cycloaliphatique hydrophobe flexibilisée chargée durcie dans le cadre de cette utilisation présente les mêmes propriétés que celles obtenues ci-dessus.The present invention relates generally to the use, as defined in claim 29, of a cured loaded flexibilized hydrophobic cycloaliphatic epoxy resin obtained by curing a mixture comprising from 25 to 75% by weight of inorganic filler, preferably from 30 to 70% by weight of mineral filler, preferably from 40 to 60% by weight of inorganic filler, more preferably from 45 to 55% by weight of inorganic filler, for example 50% by weight, an epoxy resin hydrophobic cycloaliphatic and a hardener for the manufacture of an electrical insulator, in particular for the manufacture of the outer sheath of an insulator, this sheath may be provided with fins or not. The loaded flexibilized hydrophobic cycloaliphatic epoxy resin cured in the course of this use has the same properties as those obtained above.

Cette utilisation permet à la fois de simplifier les procédés de l'art antérieur et de résoudre les inconvénients précités. La charge minérale permet à la fois d'améliorer la tenue au cheminement et à l'érosion du matériau.This use makes it possible at the same time to simplify the processes of the prior art and to solve the aforementioned drawbacks. The mineral filler makes it possible both to improve the tracking behavior and the erosion of the material.

Comme indiqué ci-dessus, selon l'invention, la résine chargée peut être utilisée pour fabriquer uniquement la gaine de l'isolateur, munie ou non d'ailettes, par exemple en remplacement des matériaux à base de silicone de l'art antérieur, ou pour fabriquer le tube, la gaine et les ailettes de l'isolateur, par exemple lorsque le tube est constitué d'un arrangement de fibres.As indicated above, according to the invention, the filled resin can be used to manufacture only the sheath of the insulator, provided or not with fins, for example to replace the silicone-based materials of the prior art, or to manufacture the tube, the sheath and the fins of the insulator, for example when the tube consists of a fiber arrangement.

Dans le cas où la gaine est munie d'ailettes, la présente invention peut consister par exemple à mouler lesdites ailettes sur un tube, le tube pouvant par exemple être constitué d'un arrangement de fibres renforcées par une résine époxyde identique ou différente de celle utilisée pour la gaine, munie ou non d'ailettes. Le tube peut être par exemple un tube constitué de fibres renforcées par une résine époxyde tel que décrit et obtenu dans le document [1].In the case where the sheath is provided with fins, the present invention may for example consist of molding said fins on a tube, the tube may for example be constituted by an arrangement of fibers reinforced with an epoxy resin identical to or different from that used for the sheath, with or without fins. The tube may be for example a tube made of fibers reinforced with an epoxy resin as described and obtained in document [1].

La présente invention peut être mise en oeuvre par exemple dans un procédé de fabrication d'un isolateur électrique comprenant un tube creux ou plein entouré d'une gaine isolante, ladite gaine pouvant être munie d'ailettes, tel que défini dans la revendication 16.The present invention may be implemented for example in a method of manufacturing an electrical insulator comprising a hollow or solid tube surrounded by an insulating sheath, said sheath being able to be provided with fins, as defined in claim 16.

Selon un premier mode de réalisation du procédé de la présente invention, on utilise un précurseur du tube, ce précurseur étant constitué d'un arrangement de fibres tel qu'indiqué ci-dessus. Dans ce mode de réalisation, le précurseur (arrangement de fibres) est mis en place dans le moule, ledit arrangement de fibres étant imprégné de la résine chargée lors de l'étape d'introduction de ladite résine dans le moule pour former après durcissement de la résine le tube. Dans ce cas, la résine chargée forme le tube et les ailettes de l'isolateur. Dans ce cas, de préférence, un manchon est placé dans le tube formé par l'arrangement de fibres afin que la résine ne remplisse pas le tube creux.According to a first embodiment of the method of the present invention, a precursor of the tube is used, this precursor consisting of a fiber arrangement as indicated above. In this embodiment, the precursor (fiber arrangement) is placed in the mold, said fiber arrangement being impregnated with the filled resin during the step of introducing said resin into the mold to form after curing. the resin the tube. In this case, the charged resin forms the tube and the fins of the insulator. In this case, preferably, a sleeve is placed in the tube formed by the fiber arrangement so that the resin does not fill the hollow tube.

Selon un deuxième mode de réalisation de la présente invention, on utilise un tube qui est un tube en résine renforcé par un arrangement de fibres courtes ou longues de nature chimique minérale ou organique. La résine est identique ou différente de la résine chargée utilisée pour former la gaine et les ailettes. Il peut s'agir par exemple d'un tube CEVOLIT (marque de commerce) fabriqué par la société Tyco Electronics Energy. Il peut s'agir par exemple d'un tube tel que celui décrit dans le document [1]. Ce tube peut être fabriqué par exemple comme indiqué dans ce document, puis être utilisé dans le procédé de la présente invention pour fabriquer l'isolateur.According to a second embodiment of the present invention, a tube is used which is a resin tube reinforced with a short fiber arrangement. or long of chemical nature mineral or organic. The resin is the same or different from the filled resin used to form the sheath and fins. This may be for example a CEVOLIT (trademark) tube manufactured by Tyco Electronics Energy. It may be for example a tube such as that described in document [1]. This tube can be made for example as indicated in this document, and then used in the process of the present invention to manufacture the insulator.

Les matériaux utilisables dans ces procédés et le mélange sont décrits ci-dessus.The materials usable in these processes and the mixing are described above.

Selon l'invention, le moule à isolateur électrique à ailettes est de préférence en un matériau métallique, de préférence en acier inoxydable. Il est de préférence de forme cylindrique et dessine les ailettes de l'isolateur. De manière plus générale, il peut être, comme pour la forme du tube, de toute forme géométrique souhaitée, par exemple de forme cylindrique, conique, tronconique ou en tonneau ou de toute autre forme avantageuse pour son utilisation.According to the invention, the finned electric insulator mold is preferably made of a metallic material, preferably stainless steel. It is preferably of cylindrical shape and draws the fins of the insulator. More generally, it may be, as for the shape of the tube, any desired geometric shape, for example of cylindrical, conical, frustoconical or barrel shape or any other form advantageous for its use.

De tels moules peuvent être fabriqués par usinage dans la masse d'acier inoxydable à l'aide d'appareils de précision, de type fraiseuses numériques et rectifieuses numériques. Un traitement de surface de type électroérosion, polissage chimique voire polissage mécanique peut permettre d'améliorer la qualité de surface du moule, et par conséquent la qualité de surface de l'isolateur (rugosité de surface faible). Ces moules peuvent être conçus et réalisés par des sociétés telles que Techni-moules, REP France ou FAMACOM.Such molds can be manufactured by machining in the mass of stainless steel using precision devices, such as digital milling machines and digital grinders. An electroerosion, chemical polishing or even mechanical polishing surface treatment can make it possible to improve the surface quality of the mold, and consequently the surface quality of the insulator (low surface roughness). These molds can be designed and made by companies such as Techni-Molds, REP France or FAMACOM.

Avantageusement, selon l'invention, un agent de démoulage à base de silicone(s) peut être utilisé afin de faciliter le démoulage de l'isolateur. Notamment, on peut utiliser l'agent de démoulage L 94-700 (référence commerciale) de la société Kluber Chemie.Advantageously, according to the invention, a release agent based on silicone (s) can be used to facilitate the demolding of the insulator. In particular, the release agent L 94-700 (commercial reference) from Kluber Chemie can be used.

Selon l'invention, le mélange est introduit dans le moule par tout moyen approprié pour le remplir. De préférence, le mélange est injecté sous pression dans le moule, par exemple en utilisant une presse à injecter de même type que celle utilisée pour injecter le silicone dans la fabrication des isolateurs de l'art antérieur. De préférence, le mélange est injecté à chaud, pour lui permettre d'épouser plus facilement la forme du moule, par exemple à une température de 100 à 140°C. De préférence, le moule est chauffé à cette température, pour les mêmes raisons, pendant l'injection de la résine.According to the invention, the mixture is introduced into the mold by any appropriate means to fill it. Preferably, the mixture is injected under pressure into the mold, for example using an injection molding machine of the same type as that used to inject the silicone into the manufacture of the insulators of the prior art. Preferably, the mixture is injected hot, to allow it to fit more easily the shape of the mold, for example at a temperature of 100 to 140 ° C. Preferably, the mold is heated at this temperature, for the same reasons, during the injection of the resin.

Avantageusement, le mélange est injecté en plusieurs points le long de l'isolateur.Advantageously, the mixture is injected at several points along the insulator.

Le tube creux ou plein, par exemple creux à base de résine époxyde renforcé par des fibres de verre longues, est préalablement disposé dans le moule, et, de préférence maintenu à la même température que le moule (par exemple 130-140°C) afin d'avoir une bonne adhésion de la résine sur le tube. Le tube, de préférence plus long que le moule, dépasse de part et d'autre du moule.The hollow or solid tube, for example hollow based on epoxy resin reinforced with long glass fibers, is previously arranged in the mold, and preferably maintained at the same temperature as the mold (for example 130-140 ° C.) in order to have a good adhesion of the resin on the tube. The tube, preferably longer than the mold, protrudes from both sides of the mold.

Avantageusement, le mélange est maintenu à sa température de polymérisation, généralement de 120 à 140°C, par exemple pendant une durée de 4 à 10 heures.Advantageously, the mixture is maintained at its polymerization temperature, generally from 120 to 140 ° C., for example for a period of 4 to 10 hours.

Après durcissement du mélange, l'isolateur obtenu est démoulé.After curing the mixture, the insulator obtained is removed from the mold.

Selon l'invention, on peut réaliser une post-cuisson de l'isolateur, par exemple à une température de 130 à 150°C, par exemple pendant 6 à 10 heures afin d'obtenir des caractéristiques mécaniques optimales de la résine.According to the invention, it is possible to post-cure the insulator, for example at a temperature of 130 to 150 ° C., for example for 6 to 10 hours in order to obtain optimum mechanical characteristics of the resin.

L'isolateur obtenu peut subir un traitement de finissage. Dans ce traitement, le tube creux peut être découpé à la longueur finale de l'isolateur s'il est trop long. Les traces de moulage telles que des bavures à la jointure du moule peuvent être supprimées par action mécanique, par exemple par polissage mécanique.The insulator obtained can undergo a finishing treatment. In this treatment, the hollow tube can be cut to the final length of the insulator if it is too long. Molding traces such as burrs at the join of the mold can be removed by mechanical action, for example by mechanical polishing.

Enfin, un ou deux collier(s) métallique(s) peuvent être fixés de façon traditionnelle, par exemple par collage respectivement à une ou aux deux extrémité(s) de l'isolateur, par exemple avec une colle époxyde. On utilise notamment la technique du frettage où le collier métallique est dilaté en température ce qui permet d'insérer en force le tube encollé dans le collier encollé. Le rétraint du collier métallique sur le tube composite assure une bonne adhésion du collier sur le tube. Cette adhésion étant renforcée par la colle.Finally, one or two metal collar (s) can be fixed in a traditional manner, for example by gluing respectively to one or both ends of the insulator, for example with an epoxy adhesive. In particular, the hooping technique is used in which the metal collar is expanded in temperature, which makes it possible to force the glue-in tube into the glued collar. The shrinkage of the metal collar on the composite tube ensures a good adhesion of the collar on the tube. This adhesion is reinforced by the glue.

Ainsi, selon l'invention, le procédé peut comprendre en outre une étape de collage d'un ou de deux collier(s) respectivement à l'une ou aux deux extrémités de l'isolateur électrique. C'est le cas par exemple lorsque l'isolateur fabriqué est un isolateur support.Thus, according to the invention, the method may further comprise a step of bonding one or two collar (s) respectively to one or both ends of the electrical insulator. This is the case example when the manufactured insulator is a carrier insulator.

Deux colliers métalliques peuvent être fixés selon la façon décrite ci-dessus dans le cas d'un isolateur support devant être raccordé à ces deux extrémités.Two metal collars may be attached as described above in the case of a carrier insulator to be connected at both ends.

Un seul collier métallique est fixé selon la façon décrite ci-dessus dans le cas d'un isolateur utilisé comme support simple. Dans cette configuration, l'autre extrémité peut être usinée de façon à recevoir le conducteur porté au potentiel. L'usinage peut être réalisé en forme d'encoche dans le cas d'un support de barre ou on peut réaliser un perçage dans le tube pour faire passer un conducteur.A single metal collar is attached as described above in the case of an insulator used as a single support. In this configuration, the other end can be machined to receive the lead brought to the potential. The machining can be done in the form of a notch in the case of a bar support or it can achieve a bore in the tube to pass a conductor.

L'isolateur de la présente invention, par exemple tube plein ou composite/mat de verre peut être de forme cylindrique, conique, en tonneau ou toute autre forme utile pour son utilisation.The insulator of the present invention, for example solid tube or composite / glass mat may be cylindrical, conical, barrel or any other form useful for its use.

La présente invention présente notamment les avantages suivants :

  • Elle permet, du fait des matériaux et du procédé utilisés, de fabriquer un isolateur moins cher que les isolateurs de l'art antérieur,
  • Elle permet, du fait des matériaux utilisés, de fabriquer un isolateur ayant une durée de vie plus longue et une plus grande fiabilité dans des conditions sévères d'utilisation (pluie, pollution, oiseaux, rongeurs, etc.) que ceux de l'art antérieur,
  • L'isolateur est sans interface libre entre le tube creux et les ailettes car on utilise une résine époxyde pour le tube et pour les ailettes (identique ou différente)
  • L'isolateur ne présente pas de problème de vides et délaminations à l'interface ailettes/tube, ce qui améliore également sa durée de vie et lui confère une plus grande fiabilité dans des conditions sévères d'utilisation (pluie, pollution, oiseaux, rongeurs, etc.) par rapport aux isolateurs de l'art antérieur, ni de décharges partielles et de claquages à cet endroit (à savoir à l'interface ailettes/tube).
  • Elle permet de supprimer le primaire d'adhésion utilisé dans l'art antérieur pour renforcer l'adhésion à l'interface du matériau du tube creux et du matériau constituant les ailettes.
The present invention has the following advantages in particular:
  • It makes it possible, because of the materials and the method used, to manufacture a less expensive insulator than the insulators of the prior art,
  • It allows, because of the materials used, to manufacture an insulator having a longer life and greater reliability under severe conditions of use (rain, pollution, birds, rodents, etc.) than those of the art prior,
  • The insulator has no free interface between the hollow tube and the fins because a resin is used epoxy for tube and fins (same or different)
  • The insulator does not have a problem of voids and delaminations at the fins / tube interface, which also improves its service life and gives it greater reliability in severe conditions of use (rain, pollution, birds, rodents , etc.) relative to prior art insulators, or partial discharges and breakdowns at this location (ie at the fins / tube interface).
  • It eliminates the adhesion primer used in the prior art to enhance the interface adhesion of the material of the hollow tube and the material constituting the fins.

D'autres caractéristiques et avantages de l'invention apparaîtront mieux à la lecture des exemples suivants donnés bien entendu à titre illustratif et non limitatif.Other features and advantages of the invention will appear better on reading the following examples given of course by way of illustration and not limitation.

Brève description des figuresBrief description of the figures

  • Figure 1 : représentation schématique d'un isolateur à tube creux selon l'invention. Figure 1 schematic representation of a hollow tube insulator according to the invention.
  • Figure 2 : représentation schématique d'un isolateur à tube plein selon l'invention. Figure 2 : Schematic representation of a solid-tube insulator according to the invention.
ExemplesExamples Exemple 1 : fabrication d'un isolateur à tube creux selon l'inventionExample 1: Manufacture of a hollow tube insulator according to the invention A. Moule et précurseur de tube creuxA. Mold and precursor of hollow tube

Le moule utilisé est de forme cylindrique et dessine les ailettes de l'isolateur. Il est en acier. Le moule est constitué de deux coquilles jointes, ayant chacune une forme interne de moitié d'isolateur dans le sens de la longueur. Ainsi, le démoulage de l'isolateur à ailette peut se faire par simple séparation des deux coquilles.The mold used is cylindrical and draws the fins of the insulator. It is steel. The mold consists of two joined shells, each having an internal half insulator lengthwise. Thus, the demolding of the fin isolator can be done by simple separation of the two shells.

Un tube composite cylindrique creux à base de résine époxyde renforcé par des fibres de verre (sous forme de mat de fibres de verre) est disposé sur l'axe longitudinal du moule, de manière centrée. Le tube composite est plus long que le moule, il dépasse de part et d'autre du moule.A hollow cylindrical composite tube based on glass fiber reinforced epoxy resin (in the form of fiberglass mat) is arranged centrally on the longitudinal axis of the mold. The composite tube is longer than the mold, it exceeds both sides of the mold.

B. Préparation de la résine chargéeB. Preparation of the charged resin

On prépare une résine époxyde cycloaliphatique hydrophobe flexibilisée comprenant 50% en poids de charge minérale.A flexibilized hydrophobic cycloaliphatic epoxy resin comprising 50% by weight mineral filler is prepared.

Première étape : préparation de la charge :First step: preparation of the load:

La charge minérale, composée à 50% en poids de silice et 50% en poids d'alumine trihydrate (ATH) est séchée sous vide à 80°C pendant 24 heures.The inorganic filler, composed of 50% by weight of silica and 50% by weight of alumina trihydrate (ATH) is dried under vacuum at 80 ° C for 24 hours.

Deuxième étape : préparation de la résine et du durcisseur :Second step: preparation of the resin and hardener:

Une partie de la charge minérale, 15 parties en poids, préalablement séchée et dégazée, est incorporée à une résine cycloaliphatique liquide de type diglycidilester (100 parties poids) ayant une densité de 1,1. Le mélange ainsi obtenu a une densité de 1,2. Il est malaxé mécaniquement à une température comprise entre 40°C et 60°C et dégazé sous vide à une pression absolue comprise entre 1000 et 10000 Pa (entre 10 et 100 mars). On obtient un sous-produit résine + charge.Part of the mineral filler, 15 parts by weight, previously dried and degassed, is incorporated to a liquid cycloaliphatic resin of the diglycidyl ester type (100 parts by weight) having a density of 1.1. The resulting mixture has a density of 1.2. It is mechanically kneaded at a temperature between 40 ° C and 60 ° C and degassed under vacuum at an absolute pressure of between 1000 and 10000 Pa (between 10 and 100 March). A resin + filler by-product is obtained.

Le complément de la charge minérale, c'est-à-dire les 35 parties en poids restants, est incorporé à un durcisseur anhydride cycloaliphatique liquide (100 parties poids). Le mélange ainsi obtenu a une densité de l'ordre de 1,9. Il est malaxé mécaniquement à une température comprise entre 40 et 60°C et dégazé comme précédemment. On obtient un sous-produit durcisseur + charge.The balance of the inorganic filler, i.e. the remaining 35 parts by weight, is incorporated into a liquid cycloaliphatic anhydride hardener (100 weight parts). The mixture thus obtained has a density of about 1.9. It is mechanically kneaded at a temperature between 40 and 60 ° C and degassed as before. A hardener + filler by-product is obtained.

Les deux sous-produits résine + charge et durcisseur + charge sont mélangés mécaniquement ensemble jusqu'à l'obtention d'une dispersion homogène. Le mélange est effectué à une température comprise entre 40 et 60°C et dégazé comme précédemment.The two by-products resin + filler and hardener + filler are mechanically mixed together until a homogeneous dispersion is obtained. The mixing is carried out at a temperature between 40 and 60 ° C and degassed as before.

Le mélange obtenu est prêt à l'emploi pour mouler l'isolateur.The resulting mixture is ready for use to mold the insulator.

C. Introduction de la résine dans le mouleC. Introduction of the resin into the mold

Le mélange précédemment obtenu est injecté sous pression dans le moule en deux parties préalablement chauffé à la température de polymérisation de la résine, ici comprise entre 130°C et 140°C, en utilisant une presse à injecter standard pour le silicone. La température est homogène dans le moule. Le tube composite creux est maintenu à la température du moule (120-130°C) afin d'avoir une bonne adhésion de la résine sur le tube composite.The previously obtained mixture is injected under pressure into the two-part mold preheated to the polymerization temperature of the resin, here between 130 ° C. and 140 ° C., using a standard injection molding machine for the silicone. The temperature is homogeneous in the mold. The hollow composite tube is maintained at the mold temperature (120-130 ° C) in order to have a good adhesion of the resin on the composite tube.

La résine est injectée en plusieurs points le long de l'isolateur pour bien remplir les ailettes dessinées par le moule.The resin is injected at several points along the insulator to properly fill the fins drawn by the mold.

D. Durcissement de la résineD. Hardening of the resin

La résine est maintenue à la température de 130-140°C pendant une durée de 20-30 minutes pour son durcissement.The resin is maintained at a temperature of 130-140 ° C for a period of 20-30 minutes for curing.

E. Extraire l'isolateur du mouleE. Extract the insulator from the mold

L'isolateur à tube creux (1) est extrait du moule après durcissement de la résine par ouverture de celui-ci. Il est représenté schématiquement sur la figure 1 annexée. Il comprend un tube (3) entouré d'une gaine isolante (5) munie d'ailettes (7). La gaine isolante et les ailettes sont constituées de la résine époxyde cycloaliphatique hydrophobe flexibilisé chargée préparée dans cet exemple. Le tube (3) est constitué d'un mat de fibre de verre renforcé par de la résine époxyde.The hollow tube insulator (1) is extracted from the mold after curing the resin by opening it. It is represented schematically on the figure 1 attached. It comprises a tube (3) surrounded by an insulating sheath (5) provided with fins (7). The insulating sheath and the fins consist of the charged flexibilized hydrophobic cycloaliphatic epoxy resin prepared in this example. The tube (3) consists of a fiberglass mat reinforced with epoxy resin.

On applique à l'isolateur une post-cuisson à 140°C pendant 8 heures pour optimiser les caractéristiques mécaniques de la résine.The insulator is post-baked at 140 ° C for 8 hours to optimize the mechanical characteristics of the resin.

Les caractéristiques de la résine obtenue sont indiquées dans le tableau ci-dessous.The characteristics of the resin obtained are indicated in the table below.

Le tube creux est ensuite découpé à la longueur finale de l'isolateur.The hollow tube is then cut to the final length of the insulator.

Les traces de moulage telles que des bavures à la jointure du moule sont supprimées par polissage.Molding traces such as burrs at the join of the mold are removed by polishing.

Un ou deux colliers métalliques sont alors fixés de façon traditionnelle par collage aux deux extrémités de l'isolateur. Le nombre de collier métallique dépend de l'application de l'isolateur. De même, une extrémité peut être usinée pour supporter un conducteur.One or two metal collars are then fixed in a traditional way by bonding to both ends of the insulator. The number of metal clamps depends on the application of the insulator. Similarly, one end can be machined to support a conductor.

L'isolateur obtenu est utilisable dans une application haute tension.The insulator obtained can be used in a high voltage application.

Un autre essai est réalisé où la charge minérale est constituée de 25 % en poids d'alumine trihydrate (ATH) et de 25 % en poids de silice. Un isolateur électrique utilisable dans une application haute tension est obtenu. Tableau des caractéristiques de la résine flexibilisée hydrophobe chargée obtenue dans cet exemple Caractéristiques Unité Norme Valeur Taux de charge total (en poids) % 50 Taux de charge ATH (en poids) % 25 Temps de gélification à 110°C 8'20" Dureté Shore A DIN53505 99 Température de transition vitreuse (DSC) °C ISO11457-2 18-30 Résistance à la traction à 23°C MPa ISO 527 17 Allongement à la rupture à 23°C % ISO527 19,4 Module d'élasticité en traction à 23°C MPa ISO527 1175 Résistance à la traction à -25°C MPa ISO527 45 Allongement à la rupture à -25°C % ISO527 1,5 Module d'élasticité en traction à -25°C MPa ISO527 7764 Rigidité diélectrique kW/mm CEI 60243 23 Résistance à l'arc s CEI 61621 / ASTM D495 220 Résistance au cheminement et à l'érosion CEI 60587 1 B4.5 (Mesures effectuées sur la résine chargée durcie) Another test is carried out wherein the inorganic filler consists of 25% by weight of alumina trihydrate (ATH) and 25% by weight of silica. An electrical isolator for use in a high voltage application is obtained. Table of characteristics of the hydrophobic charged flexibilized resin obtained in this example Characteristics Unit Standard Value Total charge rate (by weight) % 50 ATH charge rate (by weight) % 25 Gel time at 110 ° C 8'20 " Hardness Shore A DIN53505 99 Glass transition temperature (DSC) ° C ISO11457-2 18-30 Tensile strength at 23 ° C MPa ISO 527 17 Elongation at break at 23 ° C % ISO527 19.4 Tensile modulus of elasticity at 23 ° C MPa ISO527 1175 Tensile strength at -25 ° C MPa ISO527 45 Elongation at break at -25 ° C % ISO527 1.5 Tensile modulus at -25 ° C MPa ISO527 7764 Dielectric strength kW / mm IEC 60243 23 Resistance to the arc s IEC 61621 / ASTM D495 220 Resistance to tracking and erosion IEC 60587 1 B4.5 (Measurements performed on the cured filled resin)

Exemple 2 : procédé de fabrication d'un isolateur à tube plein selon l'inventionExample 2: Process for manufacturing a solid-tube insulator according to the invention

On utilise le même protocole que celui décrit dans l'exemple 1 pour la fabrication de la résine chargée et de l'isolateur, mais on remplace le tube creux par un tube plein.The same protocol as that described in Example 1 is used for the production of the charged resin and the insulator, but the hollow tube is replaced by a solid tube.

On obtient un isolateur électrique (1) conforme à la présente invention. Cet isolateur est représenté sur la figure 2 annexée. Il comprend le tube plein (3') entouré d'une gaine isolante (5) munie d'ailettes (7).An electrical isolator (1) according to the present invention is obtained. This insulator is represented on the figure 2 attached. It comprises the solid tube (3 ') surrounded by an insulating sheath (5) provided with fins (7).

La gaine isolante et les ailettes sont constituées de la résine époxyde cycloaliphatique hydrophobe flexibilisée chargée préparée.The insulating sheath and the fins are made from the prepared loaded flexibilized hydrophobic cycloaliphatic epoxy resin.

Le tube (3') est une tige constituée de résine époxyde renforcée par un arrangement de fibres de verre.The tube (3 ') is a rod made of epoxy resin reinforced by a fiberglass arrangement.

Cet isolateur convient par exemple pour être utilisé dans les supports de lignes hautes tensions aériennes.This isolator is suitable for example for use in high voltage line supports air.

Liste des référencesList of references

  1. [1] EP-A-1091365 (Axicom AG, Zeigniederlassung Wohlen).[1] EP-A-1091365 (Axicom AG, Zeigniederlassung Wohlen).
  2. [2] WO 02/061767 (MC-GRAW-EDISON COMPANY).[2] WO 02/061767 (MC-GRAW-EDISON COMPANY).
  3. [3] CIGRE N°184 d'avril 2001 « Composite Insulator Handling Guide » ou dans la publication suivante : « IEEE Task Force Report : Brittle Fracture in Nonceramic Insulators », IEEE Transactions on Power Delivery, Vol 17, N°3, July 2002, pp 848-856 .[3] CIGRE N ° 184 April 2001 "Composite Insulator Handling Guide" or in the following publication: "IEEE Task Force Report: Brittle Fracture in Nonceramic Insulators," IEEE Transactions on Power Delivery, Vol 17, No. 3, July 2002, pp 848-856 .
  4. [4] « Hydrophobic cycloaliphatic epoxy : Latest findings and future developments », Christian Beisele, 2001 World Insulator Congress and Exhibition, 18-21 November, Shangai, CHINA .[4] "Hydrophobic cycloaliphatic epoxy: Latest findings and future developments", Christian Beisele, 2001 World Insulator Congress and Exhibition, 18-21 November, Shanghai, China .

Claims (30)

  1. Electrical insulator (1) comprising a solid or hollow tube (3) surrounded by an insulating sheath (5), characterized in that the insulating sheath is composed of a filled, hardened, flexibilised hydrophobic cycloaliphatic epoxy resin obtained by hardening a mixture comprising: 25 to 75% by weight of mineral filler, a hydrophobic cycloaliphatic epoxy resin and a hardener;
    wherein the filled, hardened, flexibilised, hydrophobic cycloaliphatic epoxy resin has the following properties:
    - glass transition temperature: 0 to 50°C; preferably 10 to 30°C; more preferably 18 to 30°C;
    - breaking stress: 14 to 40 MPa;
    - modulus of elasticity: 200 to 4000 MPa;
    - elongation at break: 10 to 30%;
    and wherein the filled, hardened, flexibilised, hydrophobic cycloaliphatic epoxy resin also has:
    - SHORE A hardness equal to or greater than 98 and/or
    - resistance to tracking and erosion equal to or greater than class 1A3.5 or 1B3.5 according to standard IEC 60587.
  2. Electrical insulator according to claim 1, wherein the mixture comprises 30 to 70 wt.% of mineral filler, preferably 40 to 60 wt.% of mineral filler, more preferably 45 to 55 wt.% of mineral filler, e.g. 50 wt.% of mineral filler.
  3. Electrical insulator according to claim 1, wherein the mineral filler comprises 25 to 75% by weight of alumina trihydrate, the remainder being composed of at least one other filler material.
  4. Electrical insulator according to claim 3, wherein the other filler material is chosen from the group comprising alumina, silica, calcium oxide, magnesium oxide, silicon fluoride, wollastonite, calcium carbonate, titanium oxide, nanoparticles of clay or a mixture of two or more of these materials.
  5. Electrical insulator according to claim 1, wherein the mineral filler comprises 25 to 75% by weight of alumina trihydrate, preferably 40 to 60% by weight of alumina trihydrate, the remainder being composed of alumina or silica or of a mixture of alumina and silica.
  6. Electrical insulator according to claim 1, wherein the mineral filler is a mixture of a micronic sized filler and a submicronic sized filler.
  7. Insulator according to claim 1, wherein the mixture further comprises from 5 to 10% by weight of elastomeric spheres.
  8. Insulator according to claim 1, wherein the mixture further comprises one or several additives, chosen from among a polysiloxane with -OH terminations, a polysiloxane/polyether copolymer and a cyclic polysiloxane or a mixture of two or three of these polysiloxanes.
  9. Insulator according to claim 1, wherein the solid or hollow tube is composed of an arrangement of fibers in the form of a tube.
  10. Insulator according to claim 9, wherein the arrangement of fibers is composed of an arrangement of fibers chosen from among a mat of fibers or a fabric of single-dimensional, two-dimensional or three-dimensional fibers.
  11. Insulator according to claim 9, wherein the arrangement of fibers is impregnated with a hydrophobic cycloaliphatic epoxy resin comprising 25 to 75% by weight of mineral filler and a hardener.
  12. Insulator according to claim 11, wherein the fibers are chosen from among mineral fibers such as glass fibers, quartz fibers, silicon carbide fibers, or from among organic fibers such as aramid fibers, polyester fibers, and polybenzobisoxazole fibers.
  13. Insulator according to any one of claims 1 to 8, wherein the solid or hollow tube is made from a resin filled with a particular organic or inorganic reinforcement.
  14. Insulator according to any one of claims 1 to 8, wherein the solid or hollow tube is made from a resin filled with alumina, silica or a mixture of alumina and silica.
  15. Insulator according to claim 1, wherein the tube is chosen from among a straight tube, a conical tube, a tapered tube, a barrel-shaped tube, and a tube with a combination of these shapes.
  16. Process for manufacturing an electrical insulator comprising a solid or hollow tube surrounded by an insulating sheath, wherein said sheath may be provided with fins, characterized in that it comprises the following steps:
    - installing the insulator tube, or when the tube is a hollow tube, install a precursor of the tube optionally composed of an arrangement of fibers forming a tube, in an electrical insulator mould, possibly with fins,
    - feeding a mixture in the mould, comprising: 25 to 75% by weight of a mineral filler, a hydrophobic cycloaliphatic epoxy resin and a hardener so as to form the sheath, and possibly its fins, around said tube or its precursor,
    - hardening the mixture fed into the mould so as to obtain a filled, hardened, flexibilised, hydrophobic, cycloaliphatic epoxy resin, and thereby obtain the insulator, and
    - extracting the insulator obtained from the mould;
    wherein the filled, hardened, flexibilised, hydrophobic, cycloaliphatic epoxy resin has the following properties:
    - glass transition temperature: 0 to 50°C; preferably 10 to 30°C; more preferably 18 to 30°C;
    - breaking stress: 14 to 40 MPa;
    - modulus of elasticity: 200 to 4000 MPa;
    - elongation at break: 10 to 30%;
    and wherein the filled, hardened, flexibilised, hydrophobic, cycloaliphatic resin also has:
    - SHORE A hardness equal to or greater than 98, and/or
    - resistance to tracking and erosion equal to or greater than class 1A3.5 or 1B3.5 according to IEC standard 60587.
  17. Process according to claim 16, wherein the mixture contains 30 to 70 wt.% of mineral filler, preferably 40 to 60 wt.% of mineral filler, more preferably 45 to 55 wt.% of mineral filler, e.g. 50 wt.% of mineral filler.
  18. Process according to claim 16, wherein the mineral filler comprises 25 to 75% by weight of alumina trihydrate, the remainder being composed of at least one other filler material.
  19. Process according to claim 16, wherein the other filler material is chosen from the group comprising alumina, silica, calcium oxide, magnesium oxide, silicon fluoride, wollastonite, calcium carbonate, titanium oxide, nanoparticles of clay or a mixture of two or more of these materials.
  20. Process according to claim 16, wherein the mineral filler comprises 25 to 75% by weight of alumina trihydrate, preferably 40 to 60% by weight of alumina trihydrate, the remainder being composed of alumina or silica or of a mixture of alumina and silica.
  21. Process according to claim 16, wherein the mineral filler is a mixture of a micronic sized filler and a submicronic sized filler.
  22. Process according to claim 16, wherein the mixture further comprises from 5 to 10% by weight of elastomeric spheres.
  23. Process according to claim 16, wherein the mixture further comprises a polysiloxane with -OH terminations, a polysiloxane/polyether copolymer and/or a cyclic polysiloxane.
  24. Process according to claim 16, wherein a precursor of the tube is installed in the mould, this precursor is composed of an arrangement of fibers forming a hollow tube, the arrangement of fibers being chosen from among a mat of fibers or a fabric of single-dimensional, two-dimensional or three-dimensional fibers.
  25. Process according to claim 24, wherein the fibers are chosen from the group comprising mineral fibers such as glass fibers, quartz fibers, silicon carbide fibers, or from among organic fibers such as aramid fibers, polyester fibers, and polybenzobisoxazole fibers.
  26. Process according to claim 16, wherein a precursor of the tube is installed in the mould, this precursor is composed of an arrangement of fibers forming a hollow tube, the arrangement of fibers being impregnated with the filled unhardened hydrophobic cycloaliphatic epoxy resin during the step in which the said resin is fed in the mould to form the tube and the sheath after hardening of the resin.
  27. Process according to any one of claims 16 to 26, wherein the tube is chosen from a straight tube, a conical tube, a tapered tube, a barrel-shaped tube, and a tube with a combination of these shapes.
  28. Process according to claim 16, further comprising a step to glue one or two collars to one or to both ends, respectively, of the electrical insulator.
  29. Use of a filled, hardened, flexibilised, hydrophobic, cycloaliphatic epoxy resin obtained by hardening a mixture containing: 25 to 75% by weight of mineral filler, a hydrophobic cycloaliphatic epoxy resin and a hardener for the manufacture of an electrical insulator according to Claim 1;
    wherein the filled, hardened, flexibilised, hydrophobic, cycloaliphatic epoxy resin has the following properties:
    - glass transition temperature: 0 to 50°C; preferably 10 to 30°C; more preferably 18 à 30°C;
    - breaking stress: 14 to 40 MPa;
    - modulus of elasticity: 200 to 4000 MPa;
    - elongation at break: 10 to 30%;
    and wherein the filled, hardened, flexibilised, hydrophobic, cycloaliphatic epoxy resin also has:
    - SHORE A hardness equal to or greater than 98, and/or
    - resistance to tracking and erosion equal to or greater than class 1A3.5 ou 1B3.5 according to IEC standard 60587.
  30. Use according to claim 29, wherein the mixture comprises 30 to 70 wt.% of mineral filler, preferably 40 to 60 wt.% of mineral filler, further preferably 45 to 55 wt.% of mineral filler, e.g. 50 wt.% of mineral filler.
EP06792535.4A 2005-07-20 2006-07-20 Electric insulator and a method for the production thereof Not-in-force EP1905046B1 (en)

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Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2868875B1 (en) * 2004-04-07 2011-09-23 Areva T & D Sa ELECTRICAL APPARATUS COMPRISING A COMPOSITE INSULATOR HAVING A CONTACTS OBSERVATION WINDOW
WO2009073901A2 (en) * 2007-12-05 2009-06-11 Corrine Jean Greyling A polymeric high voltage insulator with a hard, hydrophobic surface
US20100078198A1 (en) * 2008-08-13 2010-04-01 John Richardson Harris High Gradient Multilayer Vacuum Insulator
EP2182527A1 (en) * 2008-10-31 2010-05-05 ABB Research Ltd. Insulating hollow body for a high voltage insulator
FR2941811A1 (en) * 2009-01-30 2010-08-06 Areva T & D Sa Electric insulator for e.g. non-conventional instrument transformer, has optical fibers placed along external surface of body, and insulated material cover surrounding body, where optical fibers are housed in cured epoxy resin protection
JP5679561B2 (en) * 2011-02-23 2015-03-04 矢崎総業株式会社 Plastic molded product
RU2499317C2 (en) * 2012-02-21 2013-11-20 Общество с ограниченной ответственностью "Инвест-Энерго" Method to apply hydrophobic coating of equal thickness onto electric insulating structure
RU2496168C1 (en) * 2012-02-21 2013-10-20 Общество с ограниченной ответственностью "Инвест-Энерго" Electric-insulating structure with water-proof coating with even thickness
WO2018044284A1 (en) * 2016-08-31 2018-03-08 Ofs Fitel, Llc Multi-fiber optical distribution cable for hallway installations
CN108122650A (en) * 2016-11-29 2018-06-05 黄璜 The special-shaped bushing pipe of change can be fitted
FR3067164B1 (en) 2017-06-02 2019-08-02 Sediver Sa PROCESS FOR TREATING A SUPER-HYDROPHOBIC PROTECTIVE COATING COMPONENT IN GLASS OR PORCELAIN
CN109143510B (en) * 2018-10-15 2024-01-05 富通集团（嘉善）通信技术有限公司 Method and system for continuously producing optical cable
FR3091406B1 (en) * 2018-12-31 2021-01-15 Centre National De Recherche Scient Cnrs Material for electrical insulation and manufacturing process
US11227708B2 (en) 2019-07-25 2022-01-18 Marmon Utility Llc Moisture seal for high voltage insulator
RU2714682C1 (en) * 2019-08-27 2020-02-19 Акционерное общество «Южноуральский арматурно-изоляторный завод» Electric insulating structure with hydrophobic coating
CN112280247A (en) * 2020-10-29 2021-01-29 西安永兴科技发展有限公司 High-temperature-resistant high-humidity-heat-resistant fiber-reinforced composite material and preparation method thereof
US11916448B2 (en) 2021-02-01 2024-02-27 The Timken Company Small-fraction nanoparticle resin for electric machine insulation systems
CN113345659A (en) * 2021-03-25 2021-09-03 天津大学 Basin-type insulator surface charge prevention and control method based on flexible coating
CN113593794B (en) * 2021-07-01 2023-08-08 搏世因（北京）高压电气有限公司 Automatic pressure gel pure dry type capacitor type high-voltage insulating sleeve and manufacturing method thereof

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1172048A (en) * 1967-06-12 1969-11-26 Westinghouse Electric Corp Crack Resistant Epoxy Resin Casting Composition
US3645899A (en) 1968-08-19 1972-02-29 Ohio Brass Co Molded epoxy resin electrical insulating body containing alumina and silica
GB1233310A (en) * 1969-08-04 1971-05-26
US4259545A (en) * 1979-12-31 1981-03-31 Hayden Robert K High voltage safety-glow insulator
GB2147225B (en) 1983-09-28 1987-02-25 Richard Hall Clucas Method of manufacturing coated resin bonded glass fibre rods
US4810836A (en) * 1987-06-03 1989-03-07 Ngk Insulators, Ltd. Optical fiber-containing insulators
JPH0664953B2 (en) * 1988-08-10 1994-08-22 日本碍子株式会社 Insulator with built-in optical fiber and manufacturing method thereof
FR2725302B1 (en) * 1994-09-30 1997-03-14 Sediver AN ELECTRICAL ISOLATOR EQUIPPED WITH OPTICAL FIBERS AND ITS MANUFACTURING METHOD
EP0899304B1 (en) * 1997-08-27 2005-03-16 Huntsman Advanced Materials (Switzerland) GmbH Hydrophobic epoxy resin composition
US6049946A (en) * 1998-06-08 2000-04-18 Newell Operating Company Adjustable hinge
JP4823419B2 (en) 1998-12-09 2011-11-24 ハンツマン アドバンスト マテリアルズ （スイッツァランド） ゲーエムベーハー Hydrophobic epoxy resin
WO2000055254A1 (en) * 1999-03-16 2000-09-21 Vantico Ag Hardenable composition with a particular combination of characteristics
DE59912714D1 (en) 1999-10-07 2005-12-01 Axicom Ag Zweigniederlassung W Process for producing a hollow composite insulator
US6657128B2 (en) 2001-01-29 2003-12-02 Mcgraw-Edison Company Hydrophobic properties of polymer housings

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BEISELE C: "Hydrophobic cycloaliphatic epoxy latest findings and future developments", WORLD INSULATOR CONGRESS AND EXHIBITION PROCEEDINGS, 2001, pages 141 - 153 *

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EP1905046A1 (en) 2008-04-02
WO2007010025A1 (en) 2007-01-25
US7989704B2 (en) 2011-08-02
US20080296046A1 (en) 2008-12-04

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