EP1769511B1 - Verfahren zur herstellung eines isolators für hochspannungsanwendungen - Google Patents

Verfahren zur herstellung eines isolators für hochspannungsanwendungen Download PDF

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Publication number
EP1769511B1
EP1769511B1 EP05789994A EP05789994A EP1769511B1 EP 1769511 B1 EP1769511 B1 EP 1769511B1 EP 05789994 A EP05789994 A EP 05789994A EP 05789994 A EP05789994 A EP 05789994A EP 1769511 B1 EP1769511 B1 EP 1769511B1
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Prior art keywords
reinforcement
production method
micron
particles
insulator
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French (fr)
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EP1769511A1 (de
Inventor
Jean-Luc 16 chemin de la Mollarde BESSEDE
Abderrahmane Beroual
Nicole Chalet No. 61 ALBEROLA
Lionel Flandin
Nadège BARREAUD
Laëtitia VOUYOVITCH
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Grid Solutions SAS
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Areva T&D SAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/292—Protection against damage caused by extremes of temperature or by flame using material resistant to heat
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • 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
    • 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 invention relates to a method of manufacturing an insulator from a high performance solid dielectric material for use in high voltage electrical devices.
  • the invention relates to a method of manufacturing an electrical insulator for use in high voltage made from a composite material based on a polymer matrix reinforced with a mineral filler.
  • the mineral filler is composed of a micron-sized mineral filler and a submicron-type mineral filler. These fillers of different sizes may be of different chemical compositions.
  • the micron and submicron charges may be composed of several types of charges of different chemical compositions.
  • the polymer matrix may advantageously be a thermosetting resin reinforced with a mineral filler, an epoxy resin filled with alumina, or a silicone matrix reinforced with a trihydrated alumina.
  • High voltage means a voltage greater than 1000 volts.
  • a material To be used as insulation in high voltage electrical devices, a material must have particular dielectric properties, namely high dielectric strength as well as low permittivity and dielectric losses. In particular, the material must have a maximum dielectric strength both in a very homogeneous field and in a strong divergent field. In addition, these materials must have good thermo-mechanical and thermal behavior.
  • insulating materials are generally obtained by adding mineral fillers in the polymer matrix of the material.
  • composites based on thermosetting resins such as epoxy resins reinforced with glass fibers, silicones reinforced with mineral fillers, vinyl resins, unsaturated polyesters, or composites based on thermoplastic matrices such as polyethylenes, polycarbonates, polyesters or polytetrafluoroethylenes.
  • thermoplastic matrices such as polyethylenes, polycarbonates, polyesters or polytetrafluoroethylenes.
  • these materials are particularly used in the field of high voltage transformers, high voltage circuit breakers and power capacitors as insulating walls, insulating supports or insulating bushings.
  • the insulating cones used in circuit breakers or gas-insulated cables are made of alumina-loaded epoxy resin.
  • dry type distribution transformers which are isolated by charged epoxy resins, or the insulators supporting high voltage overhead lines. which are composed of a glass fiber composite tube impregnated with epoxy resin and are covered with aluminum fins loaded with alumina trihydrate.
  • the addition of the mineral reinforcement to the polymer matrix has the consequence, inter alia, of improving the thermomechanical resistance and the thermal conductivity of the material.
  • the material in the case where the material is to be used in an electrical device, more specifically in the case of an insulator for high-voltage switchgear, it is particularly advantageous to improve the thermal conductivity properties of the material.
  • the addition of charge has a contrasting effect on the dielectric properties of the material by inducing, on the one hand, an increase in its dielectric strength in divergent field due to a barrier effect played by the charges and, on the other hand, a decrease in its dielectric strength in a homogeneous field resulting from a strengthening of the electric field in the matrix caused by the presence of the charges of lower electrical resistivity.
  • the sizing of certain insulators is calculated according to the mechanical stresses applied to the insulators and the mechanical characteristics of the material, in particular the thermomechanical characteristics of the material.
  • the polymer matrix is chosen from materials with strong mechanical characteristics, such as epoxy resins. It follows from the mechanical design of the insulators that the applied dielectric stresses are relatively small compared to the limiting dielectric characteristics of the material. As a result, a high safety factor is applied in the dielectric field.
  • the reduction of the dielectric strength of the homogeneous field material does not affect the overall behavior of the material and therefore its application.
  • a high safety coefficient is applied in the dielectric domain, electrical failures inducing the dielectric breakdown of the insulator can be observed in operation.
  • These dielectric breaks are generally due to electrical aging leading to internal heating of the material, including the presence of partial discharges.
  • the partial discharges in the material under electrical stresses are initiated preferentially at the level of defects such as cavities, micro-cavities, dust, metal inclusions or casting defects, following a local reinforcement of the field.
  • the destructive effect of the partial discharges, which generate a local heating of the material is reduced by dissipation of energy in the material.
  • the material has a better aging resistance.
  • the applied dielectric stresses are strong.
  • the polymer matrix is chosen from materials with strong dielectric characteristics such as, for example, silicones reinforced with a mineral filler.
  • thermosetting resins reinforced with mineral fillers in particular thermosetting resins reinforced with mineral fillers, resins epoxides loaded with alumina or silica, or silicones loaded with alumina trihydrate, are particularly used in medium and high voltage applications because they have very good thermomechanical and dielectric properties.
  • these composite materials, described above are reinforced by micron-sized mineral fillers, including mixtures of micron-size fillers of different chemical compositions.
  • this document [2] of the prior art compares three methods of dispersion using a ball-milling process, which consists in providing the energy necessary for the dispersion of the reinforcing agglomerates by the interception of balls.
  • the first two methods less effective, break up the reinforcing agglomerates with or without a solvent, before the introduction of the reinforcement into the resin.
  • the third method judged to be more effective in obtaining good dispersion, uses the "ball-milling" method to directly dispersing a submicron alumina in a mixture comprising epoxy resin (without hardener) and solvent. The solvent is subsequently removed.
  • the disadvantage of this method is that the high viscosity of the mixture of the resin and alumina does not allow to have alumina concentrations greater than 10% by volume.
  • the properties of a given material can be improved by using this dispersion mode only up to the maximum addition of 10% by volume of a reinforcement.
  • Another method used to disperse a reinforcement in a resin matrix is to use vibrations caused by ultrasound (sound frequencies above 20 kHz). These ultrasounds provide the "matrix reinforcement-resin" system with the energy necessary to break the interactions that bind the reinforcing particles together and to disperse them directly into the matrix of the resin (see document [3] ). The problem is that this technique is accompanied by a strong self-heating. In addition, the dispersion obtained by ultrasound is not very good (see document [4] ). Moreover, the document [3] shows that the adhesion of the reinforcement on the matrix is quite weak for the samples made using ultrasound. Indeed, in their work, the authors do not observe any size effect during mechanical fracture tests for samples made using ultrasound.
  • the object of the invention is to improve the electrical properties of a composite dielectric material loaded with a specific reinforcement in order to obtain a high performance insulator.
  • it is sought to improve the thermal conductivity, the dielectric strength in a diverging field, the resistance to partial discharges and thus, consequently, to improve the resistance over time of the dielectric strength of the material of the insulator so that it is more suitable for use in high voltage applications.
  • the object of the invention is also to provide a method for obtaining an insulator having improved dielectric properties. This is possible because the process allows to obtain a polymer matrix composition loaded with a mineral reinforcement in which the reinforcement is uniformly dispersed within the composition. In particular, the process according to the invention makes it possible to uniformly disperse in the matrix a maximum reinforcement level of 45% by volume.
  • the first type of mineral reinforcement includes particles of one or more micron-sized dielectric materials and the second type of reinforcement comprises particles of one or more dielectric materials of submicron size, these particles of different sizes may be of different chemical composition.
  • a hardener is a reactive product used to cause the hardening of the resin.
  • the first step of mechanical mixing of the hardener and the submicron-size reinforcing particles, prior to mixing with the epoxy resin and the determined amount of micron-sized reinforcing particles, makes it possible to obtain a good dispersion of the submicron size reinforcement in the hardener.
  • the particles of the submicron-sized mineral reinforcement have a size at least two times smaller than the particle size of the micron-sized mineral reinforcement.
  • 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 Like, for example lamellar morphologies such as leaflets or rods, the notion of size refers to the largest dimension of the particle, for example the length in the case of a sheet.
  • the size of the particles of submicron size is less than or equal to one micrometer, and that the size of the micron-size particles is greater than one micrometer.
  • the particles of the micron-sized mineral reinforcement have a size of between 1 and 100 microns and the particles of the submicron-sized mineral reinforcement have a size of between at least 5 nanometers and at most a few hundred nanometers.
  • the particles of the micron-sized mineral reinforcement have a size of between 1 and 30 microns and the particles of the submicron-sized mineral reinforcement have a size of between 10 nanometers and a few hundred nanometers.
  • the particles of the micron-sized mineral reinforcement have a size of 6.6 micrometers and the particles of the submicron-sized mineral reinforcement have a size of 0.4 micrometer.
  • the reinforcements consist of at least one material chosen from alumina Al 2 O 3 , alumina trihydrate (ATH) Al (OH) 3 , calcium oxide CaO magnesium oxide MgO, silica SiO 2 , wollastonite, calcium carbonate CaCO 3 , titanium oxide TiO 2 , silicates such as montmorillonites, vermiculites, kaolin and micas or a mixture of these different materials.
  • the compounds based on silicates are nanocharges of silicate type ("nanoclay" in English), that is to say nanoscale charges whose size is less than or equal to a few hundred nanometers. It is thus possible to make mixtures with several types of micron charges and several types of submicron charges.
  • a micron-sized alumina trihydrate (ATH) reinforced silicone resin composite material a micron-size silica (SiO 2 ), a sub-micron sized silica and a submicron-sized silicate nanocharge.
  • ATH micron-sized alumina trihydrate
  • SiO 2 micron-size silica
  • SiO 2 sub-micron sized silica
  • a submicron-sized silicate nanocharge it is possible to produce a micron-sized alumina (Al 2 O 3 ) reinforced epoxy resin composite material, a micron-sized titanium oxide (TiO 2 ), a submicron-sized alumina and a nanofiller.
  • silicate type nanoscale silicate type nanoscale.
  • the particles of the first and / or second type of reinforcement undergo at least one surface treatment to improve their adhesion characteristics with the polymer matrix, before being incorporated in the first or second mixture.
  • the reinforcing particles may advantageously be the subject of one or more prior treatments, such as silanization, plasma treatment or the like, in order to promote adhesion between the reinforcement and the matrix.
  • a particular pretreatment may consist, for example, of adding nanomers (polymers of nanometric size) with the nanofillers of silicate type so as to modify the structure of the charge and obtain a so-called interleaved texture (parallel clay sheets nanometric dimensions separated by nanomers) and make the surfaces compatible.
  • intercalated texture nanocharge makes it possible to obtain the finest possible dispersion of the charges by exfoliation in the polymer matrix.
  • the reinforcements are compounds based on silicates, they can undergo an intercalation treatment and chemical surface compatibilization to facilitate their exfoliation.
  • the mineral reinforcement has a purity greater than or equal to 95%.
  • the polymer matrix is a thermosetting resin.
  • this resin is chosen from epoxy resins, unsaturated polyesters, polyurethanes, silicones or polyesters.
  • the resin is a bisphenol A diglycidyl ether epoxide resin (DGEBA).
  • the polymer matrix is a thermoplastic resin.
  • this resin is chosen from polyethylenes, thermoplastic polyesters, polyethylene terephthalates, polycarbonates or polytetrafluoroethylenes.
  • the final mixture obtained comprises at least 10% by volume of reinforcement.
  • this term here includes the reinforcement of the first type and the reinforcement of the second type.
  • the final mixture obtained comprises at most 45% by volume of reinforcement.
  • the reinforcement comprises at least 1% by volume of submicron-sized mineral reinforcement and at most 99% by volume of micron-sized mineral reinforcement.
  • the final mixture obtained comprises 15% by volume of reinforcement, 25% by volume of submicron size reinforcement and 75% by volume of micron size reinforcement.
  • the amount of reinforcement added to the resin, the ratio between the submicron size reinforcement and the micron size reinforcement, as well as the chemical composition of the various reinforcing particles are suitably selected to improve the dielectric properties of the resulting final blend, i.e., of the polymer matrix composition filled with mineral reinforcement.
  • the invention also relates to a method of manufacturing an insulator for use in high voltage obtained by the manufacturing method as defined above, characterized in that the insulator has a minimum thickness of at least 10 mm.
  • High voltage means a voltage greater than 1000 V.
  • the insulator is an insulating support of dielectric material, generally used in a circuit breaker to mechanically maintain an electrically insulated conductor of the mass (outer metal shell), or mechanically maintain at least two conductors electrically insulated from each other and isolated from the mass.
  • the insulating support must perfectly maintain the position of the conductor (s) during short circuits, which induce electrodynamic forces leading to significant mechanical forces on the insulating supports.
  • the isolator is obtained by pouring the final mixture of charged polymer matrix composition into a mold, heating the mixture poured into the mold and reheating the mixture to form an insulator made of solid dielectric material having a special shape determined according to of the mold shape and having a thickness of at least 10 mm.
  • the other dimensions of the insulator are large relative to the thickness, for example at least 10 times greater than the thickness.
  • the polymer matrix may be an Araldite commercial epoxy resin CY5923 with its hardener HY5925 distributed by Huntsman.
  • the micron mineral filler may be a commercial grade WSK AT 0-30MY alumina distributed by Schwarzacher Schleifsch AG.
  • the submicron mineral filler may be a commercial grade alumina P172SB distributed by Altech Pechiney.
  • the insulator has a shape chosen from a cone, disc, and tube shape.
  • the insulator has a smooth outer surface or with a relief, for example with fins.
  • the polymer matrix may be a type of silicone HTV (high temperature vulcanization) or RTV (vulcanization at room temperature) of commercial designation ELASTOSIL distributed by Wacker.
  • the micron mineral filler may be a commercial designation SH300 alumina trihydrate distributed by Altech Pechiney.
  • the sub-micron mineral filler may be a commercial designation alumina P172SB distributed by Altech Pechiney.
  • the solid support insulator obtained according to the process of the invention has improved electrical and aging properties by incorporating micron-sized reinforcing particles and submicron-size reinforcing particles into a resin matrix, for example into epoxy resin by means of attrition milling.
  • the method according to the invention makes it possible to obtain a high voltage isolator from a resin (for example an epoxy resin) loaded with reinforcement (for example alumina) of micron and submicron sizes with a high loading rate without having to use a diluent.
  • the use of a diluent may cause contamination of the crosslinked resin matrix and thus create weak points in the insulator, such as mechanical failure, partial discharges, high local dielectric losses leading to local heating of the material forming the insulator.
  • the figure represents a SEM photograph of a dielectric material obtained according to the invention for forming a solid insulator.
  • a high voltage insulator from a composition comprising a micron-sized and submicron sized alumina-loaded epoxy resin, where the alumina reinforcement is mixed in the resin by attrition milling.
  • insulator materials according to the formulations and methods described above. These materials are obtained from identical polymer matrices but have different levels of reinforcement, as well as different submicron reinforcement / micron reinforcement ratios. Then, we performed tests in homogeneous strong field and in strong divergent field on these materials.
  • the alumina feeds have quasispherical configurations, so the notion of size refers to the "median diameter" of the particle distribution.
  • thermosetting epoxy or polyepoxide matrix matrix material is produced.
  • the resin and the hardener are mechanically mixed in the proportions recommended by the supplier.
  • the mixture is then degassed, poured into a mold and the heating and post-heating stages of the mixture are carried out.
  • control materials consisting of an epoxy resin matrix reinforced with an alumina content by volume of 15%, 25%, 35% and 45% and produced by a conventional mixing method are also produced.
  • This is an alumina having a micron size, in particular a median diameter of 6.6 ⁇ m.
  • the steps of the conventional mixing process are as follows: the epoxy resin, the hardener and the median diameter particles 6.6 ⁇ m are mechanically mixed; then we The mixture is degassed, poured into a mold and the heating and post-heating stages of the mixture are carried out.
  • the materials obtained by this conventional mixing process are referred to in Table 1 below as Method 1.
  • materials having an epoxy resin matrix reinforced by alumina content by volume of 15%, 25%, 35% and 45% of which 25% are a fraction of alumina with a median diameter of 400 nm (designated as fine alumina term), alumina content by volume of 15%, 25% and 35% of which 50% is a fine alumina fraction and finally alumina content by volume of 15%, the alumina being in full alumina of size 400 nm.
  • coarse alumina term alumina content by volume of 15%, 25% and 35% of which 50% is a fine alumina fraction
  • alumina content by volume of 15% the alumina being in full alumina of size 400 nm.
  • the mixture is degassed.
  • 50 g of epoxy resin (CY5923) and 50 g of alumina of size 6.6 ⁇ m are then poured.
  • the mixture obtained is mechanically mixed and degassed.
  • the mixture is poured into a mold and the baking steps are carried out at 140 ° C. for 20 minutes under a pressure of 1.2 bar to compensate for the shrinkage and post-baking in an oven at 140 ° C. for 8 hours of the mixture.
  • the insulator may have a conical shape, a tube or disc shape.
  • the insulator may also have asperities, such as fins, or have a smooth surface.
  • the insulator obtained is solid and has a thickness greater than or equal to 10 mm.
  • the mechanical mixtures in processes 1 and 2 are carried out using an attritor mill.
  • the mixing of the material, as well as its disintegration, is done by wear of the particles between balls set in motion in a fixed container by means of rotating blades.
  • the movement of the balls and the mixture is carried out mechanically and not by centrifugation, as would be the case in a ball-milling process.
  • the mill is a vertical device and not horizontal. The choice of a mechanical mixture is explained mainly because of the high viscosity of the mixture, which does not allow effective interception of the balls by centrifugation.
  • the parts of the apparatus for performing attrition milling i.e. the rotating blades and the inner walls of the mill, which are in contact with the alumina are preferably not metallic.
  • alumina being a highly abrasive material, it could attack the metal of the device. In this way, we avoid any possibility of metal particles being present in materials that have degraded the dielectric properties of the material.
  • the method according to the invention allows a good dispersion of the reinforcement within the matrix. There is therefore no need to use a solvent to improve the dispersion of the reinforcing particles. We thus avoids that the material produced contains traces of solvent. Indeed, after use, the solvent is evaporated, but may remain trapped in the material in the form of traces.
  • the use of solvents has the disadvantage of adding impurities in the material produced which can deteriorate the dielectric properties under strong field of the material (for example, by creating electrochemical trees). In addition, the changes made by the presence of traces of solvent are not controllable.
  • the material according to the invention is intended to be used in high voltage insulation applications in the form of solid parts, and in particular to form insulators at least 10 mm thick.
  • the different samples made are thus obtained in the form of identical plates several centimeters thick so that the studies are carried out under the same conditions as in actual use.
  • each sample is placed in a tank filled with insulating oil, between two stainless steel spheres with a diameter of 7 mm.
  • the sample is subjected to an alternating voltage of frequency 50 Hz, increasing (ramp 1 kV / s), until its breakdown (that is to say until perforation, or destruction of the material).
  • the dielectric strength of the materials follows a decreasing quasi-linear law as a function of the degree of reinforcement.
  • the addition of a submicron-sized alumina does not influence the dielectric strength of the material in a very homogeneous field.
  • the breakdown voltage of the materials is then measured under a strongly divergent field.
  • the samples to be studied are placed between a tungsten tip with a radius of curvature of 0.015 mm and a circular plane of diameter 150 mm in copper, in a tank filled with insulating oil, and the samples are subjected to an alternating voltage of frequency 50 Hz, increasing (ramp 1 kV / s), until the breakdown of the material.
  • a material is produced by mechanically mixing under vacuum between 2% and 20% by mass of nanometric filler, previously treated to present particular properties of exfoliation and consequently of dispersion in the polymer matrix (for example a nanofiller of the type designation montmorillonite commercial Nanomer I.28 E marketed by Nanocor, USA), with epoxy resin DGEBA type (commercial designation CY5923, marketed by Huntsman).
  • the nanofiller was previously passed through a sieve of mesh 75 microns, dried at 80 ° C and dispersed using a Teflon mixer to remove any aggregates of particles.
  • the resin was degassed beforehand, brought to temperature at 50 ° C. and mixed with the commercial micron load WSK AT 0-30 MY distributed bymaschineacher Schleifsch AG.
  • the micron charge was previously dried at 50 ° C.
  • the mixture thus obtained is degassed and then returned to air.
  • the hardener of anhydride type of commercial designation HY5925 distributed by Huntsman which was previously loaded by the submicron type commercial type reinforcement P172 SB distributed by Pechiney Altech.
  • the submicron charge was previously dried at 50 ° C and dispersed using a teflon mixer to remove any particulate aggregates.
  • the mixture of the resin and the hardener is at 50 ° C at atmospheric pressure.
  • the resulting mixture is degassed in three cycles with atmospheric pressure.
  • the mixture can be poured into a mold either by automated pressure gelling at the pressure of 1.2 bar or by gravity casting. In both cases the temperature of the mold is 140 ° C.
  • the material is baked in the mold at a temperature of 140 ° C for 20 minutes.
  • Micron-sized alumina particles and micron-sized montmorillonite and alumina particles were used in this example, but it should be understood that other types of reinforcement could have been used.
  • the method according to the invention allows the production of polymer matrix composite materials having reinforcement levels greater than 10% by volume for application as an insulator in the field of high voltage.
  • Obtaining reinforcement levels greater than 10% by volume is made possible by means of the process according to the invention which allows the two mineral fillers, one of submicron size and the other of micron size, to be suitably dispersed at room temperature. within the polymer matrix.
  • These mineral fillers can be composed of mixtures of fillers of different chemical compositions. This is because a large part of the submicron size charge used is a few hundred nanometers, which corresponds to a much smaller contact area than in the case of particles measuring only a few nanometers. Then, the submicron size charge is dispersed in the hardener, more fluid than the resin. The mixture obtained is therefore less viscous than if we had dispersed a large amount of particles of a few nanometers in the polymer matrix.
  • the production method makes possible a homogeneous dispersion of the reinforcement, whatever the size particles, without the need to use solvent, thus avoiding the incorporation of impurities in the material.
  • the process for producing the material according to the invention makes it possible to disperse submicron-sized mineral filler in a material, whereas it has a tendency to remain agglomerated in the prior art. This process thus makes it possible industrially to produce materials whose dielectric properties are reproducible.

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

Claims (20)

  1. Verfahren zum Herstellen eines lsolators zur Verwerdung im Hochspannungsbereich, ausgehend von einer mineralstoffverstärkten Polymermatrixzusammensetzung, dadurch gekennzeichnet, dass es die folgenden Schritte umfasst:
    - mechanisches Vermischen einer bestimmten Menge Härtungsmittel und eines mineralischen Verstärkungsmittels erster Art, das aus einem bestimmten Volumen von Teilchen eines bzw. mehrerer dielektrischer Materialien submikroskopisch kleiner Größe besteht,
    - Entgasen des so erhaltenen ersten Gemisches,
    - Beimengen einer bestimmten Menge Polymermatrix und eines mineralischen VerstärfCUngsmittels zweiter Art, das aus einem bestimmten Volumen von Teilchen eines bzw. mehrerer dielektrischer Materialien mikroskopisch kleiner Größe besteht, zu dem ersten Gemisch,
    - mechanisches Vermischen des erhaltenen zweiten Gemisches, wobei das mechanische Vermischen durch Zermahlen mittels Aneinanderreiben erfolgt,
    - Entgasen des erhaltenen Endgemisches,
    - Bilden des Isolators durch Formung des Endgemischs derart, dass der Isolator nach Erhalt eine Mindestdicke von zumindest 10 mm aufweist.
  2. Herstellungsverfahren nach dem vorangehenden Anspruch, dadurch gekennzeichnet, dass die submikroskopisch kleinen Teilchen des mineralischen Verstärkungsmittels eine Größe haben, die höchstens halb so groß wie die Größe der mikroskopisch kleinen Teilchen des mineralischen Verstärkungsmittels ist.
  3. Herstellungsverfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die mikroskopisch kleinen Teilchen des mineralischen Verstärkungsmittels eine Größe zwischen 1 und 100 µm haben und die submikroskopisch kleinen Teilchen des mineralischen Verstärkungsmittels eine Größe zwischen mindestens 5 nm und höchstens einigen Hundert nm haben.
  4. Herstellungsverfahren nach dem vorangehenden Anspruch, dadurch gekennzeichnet, dass die mikroskopisch kleinen Teilchen des mineralischen Verstärkungsmittels eine Größe zwischen 1 und 30 µm haben und die submikroskopisch kleinen Teilchen des mineralischen Verstärkungsmittels eine Größe zwischen 10 nm und einigen Hundert nm haben.
  5. Herstellungsverfahren nach dem vorangehenden Anspruch, dadurch gekennzeichnet, dass die mikroskopisch kleinen Teilchen des mineralischen Verstärkungsmittels eine Größe von 6,6 µm haben und die submikroskopisch kleinen Teilchen des mineralischen Verstärkungsmittels eine Größe von 0,4 µm haben.
  6. Herstellungsverfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass die Verstärkungsmittel aus zumindest einem Material, ausgewählt aus der Gruppe Aluminiumoxid Al2O3, Aluminiumoxid-Trihydrat (ATH) Al(OH)3, Calciumoxid CaO, Magnesiumoxid MgO, Siliciumdioxid SiO2, Wollastonit, Calciumcarbonat CaCO3, Titandioxid TiO2, Verbindungen auf Basis von Silicaten, wie etwa Montmorillonite, Vermiculite, Kaolin und Glimmer bzw. aus einem Gemisch aus diesen verschiedenen Materialien bestehen.
  7. Herstellungsverfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass die Teilchen des Verstärkungsmittels erster und/oder zweiter Art zumindest einer Oberflächenbehandlung ausgesetzt werden, um deren Hafteigenschaften mit der Polymermatrix zu verbessern, bevor sie dem ersten bzw. zweiten Gemisch beigemengt werden.
  8. Herstellungsverfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass die verwendete Polymermatrix ein wärmeaushärtendes Harz ist.
  9. Herstellungsverfahren nach dem vorangehenden Anspruch, dadurch gekennzeichnet, dass das Harz ausgewählt ist aus der Gruppe der Epoxidharze, ungesättigten Polyester, Polyurethane, Silikone oder Polyester.
  10. Herstellungsverfahren nach Anspruch 8 oder 9, dadurch gekennzeichnet, dass das Harz ein Bisphenol-A-Diglycidylether-Epoxidharz (DGEBA) ist.
  11. Herstellungsverfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die verwendete Polymermatrix ein Thermoplast-Harz ist.
  12. Herstellungsverfahren nach dem vorangehenden Anspruch, dadurch gekennzeichnet, dass das Harz ausgewählt ist aus der Gruppe der Polyethylene, thermoplastischen Polyester, Polyethylenterephtalate, Polycarbonate bzw. Polytetrafluorethylene.
  13. Herstellungsverfahren nach einem der vorangehenden Ansprüche, dadurch gekenntzeichnet, dass das erhaltene Endgemisch zumindest 10 Vol.-% an Verstärkungsmittel enthält.
  14. Herstellungsverfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass das erhaltene Endgemisch höchstens 45 Vol.-% an Verstärkungsmittel enthält.
  15. Herstellungsverfahren nach Anspruch 13 oder 14, dadurch gekennzeichnet, dass das Verstärkungsmittel mindestens 1 Vol.-% an mineralischem Verstärkungsmittel submikroskopisch kleiner Größe und höchstens 99 Vol.-% an mineralischem Verstärkungsmittel mikroskopisch kleiner Größe enthält.
  16. Herstellungsverfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass das erhaltene Endgemisch 15 Vol.-% an Verstärkungsmittel enthält, darunter 25 Vol.-% Verstärkungsmittel submikroskopisch kleiner Größe und 75 Vol.-% Verstärkungsmittel mikroskopisch kleiner Größe.
  17. Herstellungsverfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass der Schritt zum Bilden des lsolators durch Formung dadurch erhalten wird, dass
    - das erhaltene Endgemisch in eine Form gegossen wird,
    - dieses in die Form gegossene Endgemisch erhitzt wird,
    - dieses Endgemisch erneut erhitzt wird.
  18. Herstellungsverfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass es so durchgeführt wird, dass der Isolator eine Mindestdicke gleich mindestens 10 mm hat.
  19. Herstellungsverfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass es so durchgeführt wird, dass der Isolator eine Form hat, die aus einer Kegel-, Scheiben- oder Rohrform ausgewählt ist.
  20. Herstellungsverfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass es so durchgeführt wird, dass der Isolator eine Außenfläche hat, die glatt ist oder mit einem Relief versehen ist, beispielsweise mit Rippen.
EP05789994A 2004-07-13 2005-07-11 Verfahren zur herstellung eines isolators für hochspannungsanwendungen Active EP1769511B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0451513 2004-07-13
PCT/FR2005/050567 WO2006008422A1 (fr) 2004-07-13 2005-07-11 Procede de fabrication d'un isolateur pour une utilisation en haute tension

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EP1769511A1 EP1769511A1 (de) 2007-04-04
EP1769511B1 true EP1769511B1 (de) 2011-02-02

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AT (1) ATE497626T1 (de)
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Cited By (2)

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CN109970436A (zh) * 2019-04-29 2019-07-05 中材江西电瓷电气有限公司 工业氧化铝粉替代优质矾土粉干法生产支柱瓷绝缘子的配方及其制备方法和应用
WO2020016525A1 (fr) * 2018-07-20 2020-01-23 Supergrid Institute Materiau d'isolation electrique comprenant un melange de charges inorganiques micrometriques et procede de fabrication

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WO2009043376A1 (en) * 2007-10-03 2009-04-09 Abb Research Ltd Electrical insulation system with improved electrical breakdown strength
WO2010108541A1 (de) * 2009-03-25 2010-09-30 Gt Elektrotechnische Produkte Gmbh Polyurethangele und verfahren zu ihrer herstellung
EP2532010B1 (de) * 2010-02-03 2020-10-28 ABB Schweiz AG Elektrisches isolierungssystem
CN102181168B (zh) * 2011-03-08 2014-01-22 东莞华科电子有限公司 聚合物基复合材料及其制造方法
JP2014129466A (ja) * 2012-12-28 2014-07-10 Hitachi Industrial Equipment Systems Co Ltd 高電圧機器用絶縁樹脂材およびそれを用いた高電圧機器
CN103694636B (zh) * 2013-12-10 2015-12-09 中国科学院过程工程研究所 一种电气绝缘环氧树脂组合物、制备方法及其用途
WO2016101988A1 (en) * 2014-12-22 2016-06-30 Abb Technology Ag Composite formulations for direct current insulation
CN116153560B (zh) * 2023-02-28 2024-01-19 重庆大学 经表面修饰的二氧化钛纳米筛及其制备方法和在提升矿物绝缘油电气强度上的应用

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DE1907017B2 (de) * 1968-02-14 1976-04-15 Hitachi Ltd.; Hitachi Chemical Co. Ltd.; Tokio Waermehaertbare formmasse auf basis von polykondensationsharzen mit pulverfoermigen fuellstoffen
EP0348193A3 (de) * 1988-06-24 1990-09-12 Somar Corporation Epoxydharzzusammensetzung
KR950005309B1 (ko) * 1989-02-09 1995-05-23 신에쓰 가가꾸 고오교 가부시끼가이샤 반도체 봉지용 에폭시 수지 조성물 및 그 경화물
DE19963378A1 (de) * 1999-12-28 2001-07-12 Alstom Power Schweiz Ag Baden Verfahren zur Herstellung von Isolierungen elektrischer Leiter mittels Pulverbeschichtung

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Publication number Priority date Publication date Assignee Title
WO2020016525A1 (fr) * 2018-07-20 2020-01-23 Supergrid Institute Materiau d'isolation electrique comprenant un melange de charges inorganiques micrometriques et procede de fabrication
FR3084202A1 (fr) * 2018-07-20 2020-01-24 Supergrid Institute Materiau d'isolation electrique comprenant un melange de charges inorganiques micrometriques et procede de fabrication
CN109970436A (zh) * 2019-04-29 2019-07-05 中材江西电瓷电气有限公司 工业氧化铝粉替代优质矾土粉干法生产支柱瓷绝缘子的配方及其制备方法和应用

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EP1769511A1 (de) 2007-04-04
WO2006008422A1 (fr) 2006-01-26
ATE497626T1 (de) 2011-02-15

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