EP2589050A2 - Ptfe material having an anti-corona effect - Google Patents

Ptfe material having an anti-corona effect

Info

Publication number
EP2589050A2
EP2589050A2 EP11743273.2A EP11743273A EP2589050A2 EP 2589050 A2 EP2589050 A2 EP 2589050A2 EP 11743273 A EP11743273 A EP 11743273A EP 2589050 A2 EP2589050 A2 EP 2589050A2
Authority
EP
European Patent Office
Prior art keywords
ptfe
weight
lubricant
metal oxide
wetting agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP11743273.2A
Other languages
German (de)
French (fr)
Other versions
EP2589050B1 (en
Inventor
David Cade
Emmanuel Garraud
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PRODUIT PLASTIQUES PERFORMANTS HOLDING -3P HOLDING
PRODUIT PLASTIQUES PERFORMANTS HOLDING 3P HOLDING
Original Assignee
PRODUIT PLASTIQUES PERFORMANTS HOLDING -3P HOLDING
PRODUIT PLASTIQUES PERFORMANTS HOLDING 3P HOLDING
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Publication date
Application filed by PRODUIT PLASTIQUES PERFORMANTS HOLDING -3P HOLDING, PRODUIT PLASTIQUES PERFORMANTS HOLDING 3P HOLDING filed Critical PRODUIT PLASTIQUES PERFORMANTS HOLDING -3P HOLDING
Publication of EP2589050A2 publication Critical patent/EP2589050A2/en
Application granted granted Critical
Publication of EP2589050B1 publication Critical patent/EP2589050B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • H01B3/44—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 vinyl resins; acrylic resins
    • H01B3/443—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 vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds
    • H01B3/445—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 vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds from vinylfluorides or other fluoroethylenic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/06—Insulating conductors or cables
    • H01B13/08—Insulating conductors or cables by winding
    • H01B13/0891—After-treatment
    • 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
    • H01B7/02—Disposition of insulation
    • H01B7/0241—Disposition of insulation comprising one or more helical wrapped layers of insulation

Definitions

  • the present invention relates to a material based on polytetrafluoroethylene (PTFE) and its applications, such as the manufacture of electric cables.
  • PTFE polytetrafluoroethylene
  • This phenomenon also known as the corona effect, is influenced by various factors such as the nature and temperature of the material in which the discharge and the ambient air pressure take place. Indeed, when the air pressure decreases, the discharge appearance voltage also decreases. However, an airplane usually flies at an average altitude of 10,000 meters where the pressure is approximately 200 to 300 hPa. The flight conditions therefore favor the appearance of the corona effect.
  • metal oxides also known as fillers
  • titanium dioxide in extruded PTFE at levels which make it possible to obtain an anti-corona effect
  • the presence of charge within the PTFE also causes problems during the extrusion of the material, such as the increase of the extrusion pressure or the risk of breakage in the calender. These phenomena can be solved by adding lubricant to the composition. However, during the drying step, the lubricant is also likely to create pores in the material in which it is incorporated, thus leading to a low density material.
  • the present invention therefore relates to a material of polytetrafluoroethylene (PTFE), of usual density, prepared from a mixture comprising:
  • a metal oxide preferably 5 to 12% by weight, more preferably 5 to 10% by weight
  • a lubricant preferably 20 to 27% by weight
  • a wetting agent preferably 0.3 to 0.7% by weight, the percentages by weight being given with respect to the total weight of PTFE.
  • PTFE refers to unmodified or modified PTFE.
  • modified a branched PTFE whose branch is linked to the carbon chain of PTFE via an oxygen atom is targeted.
  • residual density is meant a PTFE-based material having a density greater than 1.45.
  • metal oxide refers mainly to the oxides of alkaline earth metals, transition metals and poor metals.
  • the metal oxide is selected from the group consisting of titanium dioxide, alumina, zinc oxide, copper oxide, magnesium oxide and silver oxide.
  • the PTFE material as prepared above has the following composition:
  • a metal oxide preferably 5 to 12% by weight, more preferably 5 to 10% by weight
  • the lubricant is a hydrocarbon-based liquid, such as an isoparaffinic hydrocarbon, especially Isopar TM, and the wetting agent is a fatty alcohol, preferably dodecan-1-ol.
  • the wetting agent allows a better miscibility of PTFE with the charges and thus promotes the production of a homogeneous mixture.
  • Isopar TM (Exxon Mobil Chemical) is a blend of high purity synthetic isoparaffinic hydrocarbons.
  • the material according to the invention thus makes it possible to dissipate the electrons created during the partial discharge (anti-corona effect).
  • the choice of metal oxide and lubricant percentages as well as the presence of the wetting agent makes it possible to obtain a high density final PTFE material.
  • this material can be prepared by extrusion.
  • the particle size and the specific surface area of the metal oxide particles will be controlled.
  • the material further comprises 0 to 3% by weight of a pigment.
  • the material according to the invention is in the form of a ribbon, generally several kilometers long and 3 to 400 mm wide after extrusion and cutting.
  • the ribbon will advantageously have a width of 5 to 30 mm.
  • the invention also relates to a process for manufacturing a PTFE material as described above, comprising the steps of:
  • the mixing step described above will be carried out in two stages.
  • the method will then include the following steps:
  • the process generally comprises two additional steps after extrusion:
  • the calendering is carried out at a pressure greater than 150 bar and drying at a temperature ranging from 130 to 230 ° C.
  • the ribbon can be delivered raw when it is intended to be used as raw material or cooked when it is already shaped in the finished product.
  • the cooking step is in an oven at a temperature below 450 ° C, preferably below 400 ° C.
  • the invention finally relates to the various uses of the material according to the invention.
  • the material according to the invention is an electrical insulator, particularly suitable for the manufacture of electric cables.
  • the characteristics of this material make it a material of choice for applications in the aeronautical field.
  • the invention therefore relates to an electrical cable comprising a ribbon material according to the invention, wound around a conductive core.
  • conductive core is intended to mean a strand allowing conductivity, such as a strand of copper or alumina a few millimeters in diameter, optionally treated with silver to improve the conductivity.
  • the same cable may comprise one or more conductive cores. That may be surrounded by a polyimide film, for example of Kapton® type (Dupont), before winding by one or more ribbons according to the invention.
  • a polyimide film for example of Kapton® type (Dupont)
  • the cable may be prepared using a method comprising the steps of:
  • the material according to the invention is used as an electrical insulator, in particular in the field of aeronautics. Indeed, in addition to its anticroconical effect, the material according to the invention advantageously has thermal resistance properties.
  • the process comprises 3 steps:
  • the metal oxide and PTFE powder are mixed to form the first mixture.
  • this first mixture is sieved to avoid the presence of aggregates.
  • the lubricant (Isopar), the wetting agent and optionally the pigments are then mixed to form a second mixture.
  • the second mixture is then sprayed onto the first mixture and the resulting product is then mixed again and sieved to be homogeneous.
  • Extrusion / calendering The product is then compacted to make a preform, usually a cylinder 30 cm high and 10 cm in diameter. These preforms are then extruded and then calendered to obtain a ribbon of the desired thickness (for example, 76 ⁇ " ⁇ ), which is then baked to evaporate the lubricant and is wound on a core.
  • a preform usually a cylinder 30 cm high and 10 cm in diameter.
  • These preforms are then extruded and then calendered to obtain a ribbon of the desired thickness (for example, 76 ⁇ " ⁇ ), which is then baked to evaporate the lubricant and is wound on a core.
  • Cutting / packaging This last step is used to condition the ribbon (for example, pancake or universal coil).
  • the ribbon can be delivered raw to customers. When it is used on the cable, it undergoes heat treatment at a maximum temperature of 450 ° C., preferably 380 ° C.
  • Example 1 makes it possible to obtain an exploitable ribbon contrary to Example 2.
  • the ribbon according to Example 2 has a sticky texture (delamination) and a non-homogeneous density.

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Insulating Materials (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Lubricants (AREA)

Abstract

The present invention relates to a material based on high-density polytetrafluoroethylene (PTFE) and the applications thereof, such as the manufacture of electric cables. The PTFE material according to the invention comprises PTFE, a metal oxide, a lubricant and a wetting agent.

Description

Matériau PTFE à effet anti-corona  PTFE material with anti-corona effect
La présente invention concerne un matériau à base de polytétrafluoroéthylène (PTFE) et ses applications, telles que la fabrication de câbles électriques. The present invention relates to a material based on polytetrafluoroethylene (PTFE) and its applications, such as the manufacture of electric cables.
Les récents développements de l'industrie aéronautique ont contribué à augmenter notablement le nombre des équipements électriques à bord des appareils. Par ailleurs, l'apparition des gros porteurs et le souhait de limiter l'impact des vols sur l'environnement ont conduit les constructeurs aéronautiques à rechercher des moyens pour minimiser le poids desdits appareils.  Recent developments in the aerospace industry have helped to significantly increase the number of electrical equipment on board aircraft. In addition, the appearance of large aircraft and the desire to limit the impact of flights on the environment have led aircraft manufacturers to seek ways to minimize the weight of said aircraft.
Au niveau des câbles électriques mis en oeuvre dans les appareils aéronautiques, ces tendances se sont traduites par la fabrication de câbles susceptibles de transmettre une tension de plus en plus importante sans en modifier si possible le poids ou les dimensions. Dans ces conditions, l'augmentation de la tension a eu pour conséquence de générer au sein des câbles, un phénomène de décharges partielles électriques par ionisation de l'air par avalanche. Dans ce phénomène, les électrons, soumis à un champ électrique intense, acquièrent assez d'énergie pour provoquer l'ionisation des molécules neutres (par exemple, des molécules de gaz constituants l'air) et créer ainsi de nouveaux électrons libres, également susceptibles d'ioniser d'autres molécules neutres. Lorsque la tension est suffisante, un arc électrique se produit.  At the level of the electrical cables used in aeronautical equipment, these trends have resulted in the manufacture of cables capable of transmitting more and more voltage without changing the weight or dimensions if possible. Under these conditions, the increase in voltage has resulted in the generation of cables within the cables, a phenomenon of partial electrical discharge by ionization of the air by avalanche. In this phenomenon, the electrons, subjected to an intense electric field, acquire enough energy to cause the ionization of the neutral molecules (for example, molecules of gases constituting the air) and thus to create new free electrons, also susceptible to ionize other neutral molecules. When the voltage is sufficient, an electric arc occurs.
Ce phénomène, également appelé effet corona, est influencé par divers facteurs tels que la nature et la température du matériau au sein duquel a lieu la décharge et la pression de l'air ambiant. En effet, lorsque la pression de l'air diminue, la tension d'apparition de décharge diminue également. Or, un avion vole en général à une altitude moyenne de 10 000 mètres où la pression est d'environ de 200 à 300 hPa. Les conditions de vol favorisent donc l'apparition de l'effet corona.  This phenomenon, also known as the corona effect, is influenced by various factors such as the nature and temperature of the material in which the discharge and the ambient air pressure take place. Indeed, when the air pressure decreases, the discharge appearance voltage also decreases. However, an airplane usually flies at an average altitude of 10,000 meters where the pressure is approximately 200 to 300 hPa. The flight conditions therefore favor the appearance of the corona effect.
Quand une décharge partielle a lieu au sein d'un câble comportant une âme conductrice enrobée d'un matériau isolant, ce matériau subit différentes contraintes :  When a partial discharge takes place in a cable comprising a conductive core coated with an insulating material, this material undergoes various constraints:
une contrainte thermique, due l'augmentation locale de la température dans la zone où se produit la décharge partielle,  a thermal stress, due to the local increase of the temperature in the zone where the partial discharge occurs,
- des contraintes chimiques, dues à la génération d'ozone et d'acide nitrique lors de la décharge partielle,  - chemical constraints, due to the generation of ozone and nitric acid during the partial discharge,
des contraintes mécaniques, dues à l'érosion de la surface du matériau et à l'agrandissement des pores au sein de celui-ci.  mechanical stresses, due to the erosion of the surface of the material and the enlargement of the pores within it.
Toutes ces contraintes provoquent une détérioration du matériau allant du simple vieillissement prématuré à l'apparition de fissures.  All these constraints cause deterioration of the material ranging from simple premature aging to the appearance of cracks.
La demande US 2004/0031620 décrit un câble électrique dont le matériau isolant entourant l'âme conductrice est une matrice à base de polyamideimide ou de polyesterimide à laquelle est ajoutée un oxyde de métal, le dioxyde de titane. Ce matériau permet d'éviter l'effet corona. Application US 2004/0031620 discloses an electrical cable whose insulating material surrounding the conductive core is a matrix based on polyamideimide or polyesterimide to which is added a metal oxide, titanium dioxide. This material avoids the corona effect.
Or, certaines applications nécessitent la mise en œuvre de matériau présentant à la fois des propriétés d'isolation électrique et une bonne résistance à la température, tel que le PTFE.  However, some applications require the use of material having both electrical insulation properties and good temperature resistance, such as PTFE.
Toutefois, l'introduction d'oxydes de métal (également appelées charges) telles que le dioxyde de titane dans du PTFE extrudé à des teneurs permettant d'obtenir un effet anti-corona, n'a pas été réalisée jusqu'à aujourd'hui. En effet, cette introduction soulève deux difficultés majeures :  However, the introduction of metal oxides (also known as fillers) such as titanium dioxide in extruded PTFE at levels which make it possible to obtain an anti-corona effect has not been realized until today. . Indeed, this introduction raises two major difficulties:
la présence de charges au sein du PTFE a pour conséquence de rendre le PTFE poreux et donc de conduire à l'obtention d'un matériau PTFE de faible densité. Or, afin de ne pas favoriser l'effet corona, il est nécessaire de limiter la quantité d'air présente dans le matériau et par conséquent, de minimiser le nombre de pores présents dans celui-ci.  the presence of fillers within the PTFE has the effect of rendering PTFE porous and thus lead to obtaining a low density PTFE material. However, in order not to promote the corona effect, it is necessary to limit the amount of air present in the material and therefore, to minimize the number of pores present in it.
la présence de charge au sein du PTFE entraîne par ailleurs des problèmes lors de l'extrusion du matériau, tels que l'augmentation de la pression d'extrusion ou le risque de casse au niveau du calandrage. Ces phénomènes peuvent être résolus par l'ajout de lubrifiant à la composition. Cependant, lors de l'étape de séchage, le lubrifiant est également susceptible de créer des pores dans le matériau dans lequel il est incorporé, conduisant alors à un matériau de faible densité.  the presence of charge within the PTFE also causes problems during the extrusion of the material, such as the increase of the extrusion pressure or the risk of breakage in the calender. These phenomena can be solved by adding lubricant to the composition. However, during the drying step, the lubricant is also likely to create pores in the material in which it is incorporated, thus leading to a low density material.
Le travail des inventeurs leur a permis de mettre au point un nouveau matériau à base de polytétrafluoroéthylène et d'oxyde de métal présentant un effet anti-corona et surmontant les difficultés citées ci-avant.  The work of the inventors has allowed them to develop a new material based on polytetrafluoroethylene and metal oxide having an anticonona effect and overcoming the difficulties mentioned above.
La présente invention est donc relative à un matériau à base de polytétrafluoroéthylène (PTFE), de densité usuelle, préparé à partir d'un mélange comportant :  The present invention therefore relates to a material of polytetrafluoroethylene (PTFE), of usual density, prepared from a mixture comprising:
- du PTFE,  - PTFE,
5 à 15% en poids d'un oxyde de métal, de préférence 5 à 12% en poids, plus préférentiellement encore de 5 à 10% en poids,  5 to 15% by weight of a metal oxide, preferably 5 to 12% by weight, more preferably 5 to 10% by weight,
15 à 30% en poids d'un lubrifiant, de préférence 20 à 27% en poids,  15 to 30% by weight of a lubricant, preferably 20 to 27% by weight,
0,1 à 1 % en poids d'un agent de mouillabilité, de préférence 0,3 à 0,7% en poids, les pourcentages en poids étant donné par rapport au poids total de PTFE. 0.1 to 1% by weight of a wetting agent, preferably 0.3 to 0.7% by weight, the percentages by weight being given with respect to the total weight of PTFE.
Par « PTFE », on vise un PTFE non modifié ou modifié. Par modifié, on vise un PTFE ramifié dont la ramification est liée à la chaîne carbonée du PTFE via un atome d'oxygène.  PTFE refers to unmodified or modified PTFE. By modified, a branched PTFE whose branch is linked to the carbon chain of PTFE via an oxygen atom is targeted.
Par « densité usuelle », on vise un matériau à base de PTFE ayant une densité supérieure à 1 ,45.  By "usual density" is meant a PTFE-based material having a density greater than 1.45.
Par « oxyde de métal », on vise principalement les oxydes de métaux alcalino- terreux, de métaux de transition et de métaux pauvres. Avantageusement, l'oxyde de métal est choisie parmi le groupe constitué par le dioxyde de titane, l'alumine, l'oxyde de zinc, l'oxyde de cuivre, l'oxyde de magnésium et l'oxyde d'argent.  The term "metal oxide" refers mainly to the oxides of alkaline earth metals, transition metals and poor metals. Advantageously, the metal oxide is selected from the group consisting of titanium dioxide, alumina, zinc oxide, copper oxide, magnesium oxide and silver oxide.
Une fois extrudé, le matériau PTFE tel que préparé ci-avant, présente la composition suivante :  Once extruded, the PTFE material as prepared above has the following composition:
- PTFE,  - PTFE,
5 à 15% en poids d'un oxyde de métal, de préférence 5 à 12% en poids, plus préférentiellement encore de 5 à 10% en poids,  5 to 15% by weight of a metal oxide, preferably 5 to 12% by weight, more preferably 5 to 10% by weight,
des traces d'un lubrifiant et/ou d'un agent de mouillabilité,  traces of a lubricant and / or a wetting agent,
les pourcentages en poids étant donné par rapport au poids total de PTFE. the percentages by weight being given with respect to the total weight of PTFE.
De préférence, le lubrifiant est un liquide à base d'hydrocarbures, tel qu'un hydrocarbure isoparaffinique, en particulier de l'Isopar™, et l'agent de mouillabilité est un alcool gras, avantageusement le dodécan-1 -ol. L'agent de mouillabilité permet une meilleure miscibilité du PTFE avec les charges et favorise ainsi l'obtention d'un mélange homogène.  Preferably, the lubricant is a hydrocarbon-based liquid, such as an isoparaffinic hydrocarbon, especially Isopar ™, and the wetting agent is a fatty alcohol, preferably dodecan-1-ol. The wetting agent allows a better miscibility of PTFE with the charges and thus promotes the production of a homogeneous mixture.
L'isopar™ (Exxon Mobil Chemical) est un mélange d'hydrocarbures isoparaffiniques synthétiques de grande pureté.  Isopar ™ (Exxon Mobil Chemical) is a blend of high purity synthetic isoparaffinic hydrocarbons.
Le matériau selon l'invention permet donc de dissiper les électrons créés lors de la décharge partielle (effet anti-corona). Le choix des pourcentages en oxyde de métal et en lubrifiant, ainsi que la présence de l'agent de mouillabilité permet d'obtenir un matériau PTFE final de haute densité. De plus, ce matériau peut être préparé par extrusion.  The material according to the invention thus makes it possible to dissipate the electrons created during the partial discharge (anti-corona effect). The choice of metal oxide and lubricant percentages as well as the presence of the wetting agent makes it possible to obtain a high density final PTFE material. In addition, this material can be prepared by extrusion.
Avantageusement, la granulométrie et la surface spécifique des particules d'oxyde de métal seront contrôlées. Une granulométrie comprise entre 10nm et Ι μηη, de préférence, comprise entre 150nm et 500nm sera préférée. De même, on choisira des particules d'oxyde de métal présentant une surface spécifique comprise entre 3 et 200m2/g , de préférence, comprise entre 5 et 50 m2/g. Selon un mode de réalisation de l'invention, le matériau comporte en outre 0 à 3% en poids d'un pigment. Advantageously, the particle size and the specific surface area of the metal oxide particles will be controlled. A particle size of between 10 nm and 10 nm, preferably between 150 nm and 500 nm, will be preferred. Likewise, metal oxide particles having a specific surface area of between 3 and 200 m 2 / g, preferably between 5 and 50 m 2 / g, will be chosen. According to one embodiment of the invention, the material further comprises 0 to 3% by weight of a pigment.
Pour une application dans le domaine des câbles électriques, le matériau selon l'invention se présente sous la forme d'un ruban, généralement de plusieurs kilomètres de long et de 3 à 400 mm de largeur après extrusion et découpe. Lors de sa commercialisation le ruban présentera avantageusement une largeur de 5 à 30 mm.  For an application in the field of electrical cables, the material according to the invention is in the form of a ribbon, generally several kilometers long and 3 to 400 mm wide after extrusion and cutting. When it is sold, the ribbon will advantageously have a width of 5 to 30 mm.
L'invention concerne également un procédé de fabrication d'un matériau PTFE tel que décrit ci-avant, comportant les étapes consistant à :  The invention also relates to a process for manufacturing a PTFE material as described above, comprising the steps of:
mélanger le PTFE, l'oxyde de métal, le lubrifiant, l'agent de mouillabilité et le pigment éventuel, et  mix PTFE, metal oxide, lubricant, wetting agent and any pigment, and
extruder le produit résultant de l'étape de mélange.  extruding the product resulting from the mixing step.
De préférence, l'étape de mélange décrite ci-avant s'effectuera en deux temps. Le procédé comportera alors les étapes suivantes consistant à :  Preferably, the mixing step described above will be carried out in two stages. The method will then include the following steps:
préparer un premier mélange comportant l'oxyde de métal et le PTFE en poudre, préparer un second mélange comportant le lubrifiant, l'agent de mouillabilité et le pigment éventuel,  preparing a first mixture comprising the metal oxide and the powdered PTFE, preparing a second mixture comprising the lubricant, the wetting agent and the optional pigment,
pulvériser le second mélange sur le premier mélange,  spraying the second mixture on the first mixture,
homogénéiser puis tamiser le produit résultant, et  homogenize and then sift the resulting product, and
extruder le produit résultant.  extrude the resulting product.
Ce procédé permet l'obtention d'un produit plus homogène car il limite considérablement les agrégats. Or, lors de l'étape subséquente de calandrage, la présence d'agrégats dans le matériau est un élément critique, étant donné la finesse que l'on souhaite obtenir pour le ruban final, de l'ordre de 50 à 200μηι d'épaisseur.  This process makes it possible to obtain a more homogeneous product because it considerably limits the aggregates. However, during the subsequent calendering step, the presence of aggregates in the material is a critical element, given the fineness that is desired for the final ribbon, of the order of 50 to 200μηι thick .
Comme évoqué ci-avant, le procédé comporte en général deux étapes supplémentaires après extrusion :  As mentioned above, the process generally comprises two additional steps after extrusion:
le calendrage, et  calendering, and
le séchage.  drying.
Le calendrage est réalisé à une pression supérieure à 150 bars et le séchage à une température allant de 130 à 230°C.  The calendering is carried out at a pressure greater than 150 bar and drying at a temperature ranging from 130 to 230 ° C.
Le ruban peut être livré cru lorsqu'il il est destiné à être utilisé comme matière première ou cuit lorsqu'il est déjà mis en forme dans le produit fini. L'étape de cuisson est réalisée dans un four à une température inférieure à 450°C, de préférence, inférieure à 400°C. The ribbon can be delivered raw when it is intended to be used as raw material or cooked when it is already shaped in the finished product. The cooking step is in an oven at a temperature below 450 ° C, preferably below 400 ° C.
L'invention concerne enfin les différentes utilisations du matériau selon l'invention. The invention finally relates to the various uses of the material according to the invention.
Selon une première utilisation, le matériau selon l'invention est un isolant électrique, particulièrement adapté à la fabrication de câbles électriques. En particulier, les caractéristiques de ce matériau en font un matériau de choix pour des applications dans le domaine aéronautique. According to a first use, the material according to the invention is an electrical insulator, particularly suitable for the manufacture of electric cables. In particular, the characteristics of this material make it a material of choice for applications in the aeronautical field.
L'invention vise donc un câble électrique comportant un ruban en matériau selon l'invention, enroulé autour d'une âme conductrice.  The invention therefore relates to an electrical cable comprising a ribbon material according to the invention, wound around a conductive core.
Par « âme conductrice », on vise un brin permettant la conductivité, tel qu'un brin de cuivre ou d'alumine de quelques millimètres de diamètre, optionnellement traité à l'argent pour améliorer la conductivité.  The term "conductive core" is intended to mean a strand allowing conductivity, such as a strand of copper or alumina a few millimeters in diameter, optionally treated with silver to improve the conductivity.
Un même câble peut comporter une ou plusieurs âmes conductrices. Celle(s)-ci peu(ven)t être entourée(s) d'un film polyimide, par exemple de type Kapton® (Dupont), avant enroulement par un ou plusieurs rubans selon l'invention.  The same cable may comprise one or more conductive cores. That may be surrounded by a polyimide film, for example of Kapton® type (Dupont), before winding by one or more ribbons according to the invention.
Avantageusement, le câble peut être préparé à l'aide d'un procédé comportant les étapes consistant à :  Advantageously, the cable may be prepared using a method comprising the steps of:
enrouler un ruban autour d'une âme conductrice, et,  wrap a ribbon around a conductive core, and,
cuire le câble à une température inférieure à 450°C, préférentiellement inférieure à 400°C.  bake the cable at a temperature below 450 ° C, preferably below 400 ° C.
Selon une seconde utilisation, le matériau selon l'invention est utilisé comme isolant électrique, en particulier dans le domaine de l'aéronautique. En effet, outre son effet anti- corona, le matériau selon l'invention présente avantageusement des propriétés de résistance thermique.  According to a second use, the material according to the invention is used as an electrical insulator, in particular in the field of aeronautics. Indeed, in addition to its anticroconical effect, the material according to the invention advantageously has thermal resistance properties.
L'invention sera mieux comprise à la lecture de l'exemple qui suit, donné à titre illustratif uniquement.  The invention will be better understood on reading the following example, given for illustrative purposes only.
Exemple 1 : Comparaison de deux formulations de matériau PTFE Example 1 Comparison of Two Formulations of PTFE Material
Formulations : Formulations:
Formulation 1 Formulation 2 Formulation 1 Formulation 2
PTFE poudre (kg) 10 10 Charge ZnO Al203 PTFE powder (kg) 10 10 Charge ZnO Al 2 0 3
Taux de charge (kg) 1 1  Charge rate (kg) 1 1
Granulométrie (nm) 500 100  Granulometry (nm) 500 100
Surface spécifique (m2/g) 15 10 Specific surface area (m 2 / g) 15 10
lsoparI M (kg) 2,5 2,9 lsopar IM (kg) 2.5 2.9
Densité (sur produit fini) 1 ,5 1 ,38  Density (on finished product) 1, 5 1, 38
Procédé de fabrication : Manufacturing process :
Le procédé comporte 3 étapes :  The process comprises 3 steps:
mélange,  mixed,
- extrusion / calandrage,  extrusion / calendering,
découpe / conditionnement.  cutting / conditioning.
Mélange : L'oxyde de métal et la poudre PTFE sont mélangés afin de constituer le premier mélange. Avantageusement, ce premier mélange est tamisé pour éviter la présence d'agrégats. Le lubrifiant (Isopar), l'agent de mouillabilité et éventuellement les pigments sont ensuite mélangés pour former un second mélange. Le second mélange est ensuite pulvérisé sur le premier mélange et le produit résultant est ensuite à nouveau mélangé puis tamisé pour être homogène.  Mixing: The metal oxide and PTFE powder are mixed to form the first mixture. Advantageously, this first mixture is sieved to avoid the presence of aggregates. The lubricant (Isopar), the wetting agent and optionally the pigments are then mixed to form a second mixture. The second mixture is then sprayed onto the first mixture and the resulting product is then mixed again and sieved to be homogeneous.
Extrusion / calandrage : Le produit est alors compacté pour réaliser une préforme, en général un cylindre de 30 cm de haut et de 10 cm de diamètre. Ces préformes sont ensuite extrudées puis calendrées pour obtenir un ruban de l'épaisseur désirée (par exemple, 76μη"ΐ). Ce ruban est alors passé au four afin d'évaporer le lubrifiant et est enroulé sur un noyau.  Extrusion / calendering: The product is then compacted to make a preform, usually a cylinder 30 cm high and 10 cm in diameter. These preforms are then extruded and then calendered to obtain a ribbon of the desired thickness (for example, 76μη "ΐ), which is then baked to evaporate the lubricant and is wound on a core.
Découpe / conditionnement : Cette dernière étape permet de conditionner le ruban (par exemple, en galette ou en bobine universelle).  Cutting / packaging: This last step is used to condition the ribbon (for example, pancake or universal coil).
Le ruban peut être livré cru aux clients. Lors de sa mise en œuvre sur le câble, il subit un traitement thermique à une température maximum de 450°C, préférentiellement, 380°C.  The ribbon can be delivered raw to customers. When it is used on the cable, it undergoes heat treatment at a maximum temperature of 450 ° C., preferably 380 ° C.
Conclusion : Conclusion:
L'exemple 1 permet d'obtenir un ruban exploitable contrairement à l'exemple 2. En effet, le ruban selon l'exemple 2 présente une texture collante (délamination) et de densité non homogène.  Example 1 makes it possible to obtain an exploitable ribbon contrary to Example 2. In fact, the ribbon according to Example 2 has a sticky texture (delamination) and a non-homogeneous density.

Claims

REVENDICATIONS
1 . Matériau à base de polytétrafluoroéthylène (PTFE), de densité usuelle, préparé à partir d'un mélange comportant: 1. Material of polytetrafluoroethylene (PTFE), of usual density, prepared from a mixture comprising:
- du PTFE,  - PTFE,
5 à 15% en poids d'un oxyde de métal,  5 to 15% by weight of a metal oxide,
15 à 30% en poids d'un lubrifiant,  15 to 30% by weight of a lubricant,
0,1 à 1 % en poids d'un agent de mouillabilité,  0.1 to 1% by weight of a wetting agent,
les pourcentages en poids étant donné par rapport au poids total de PTFE. the percentages by weight being given with respect to the total weight of PTFE.
2. Matériau à base de polytétrafluoroéthylène (PTFE), de densité usuelle, comportant:  2. Material based on polytetrafluoroethylene (PTFE), of usual density, comprising:
- du PTFE,  - PTFE,
5 à 15% en poids d'un oxyde de métal,  5 to 15% by weight of a metal oxide,
des traces d'un lubrifiant et/ou d'un agent de mouillabilité,  traces of a lubricant and / or a wetting agent,
les pourcentages en poids étant donné par rapport au poids total de PTFE. the percentages by weight being given with respect to the total weight of PTFE.
3. Matériau selon la revendication 1 ou 2, dans lequel le lubrifiant est un liquide à base d'hydrocarbures, tel qu'un hydrocarbure isoparaffinique.  3. Material according to claim 1 or 2, wherein the lubricant is a hydrocarbon-based liquid, such as an isoparaffinic hydrocarbon.
4. Matériau selon l'une quelconque des revendications 1 à 3, dans lequel l'agent de mouillabilité est un alcool gras tel que le dodécan-1 -ol.  4. Material according to any one of claims 1 to 3, wherein the wetting agent is a fatty alcohol such as dodecan-1-ol.
5. Matériau selon l'une quelconque des revendications 1 à 4, dans lequel l'oxyde de métal est choisie parmi le groupe constitué par le dioxyde de titane, l'alumine, l'oxyde de zinc, l'oxyde de cuivre, l'oxyde de magnésium et l'oxyde d'argent.  The material of any one of claims 1 to 4, wherein the metal oxide is selected from the group consisting of titanium dioxide, alumina, zinc oxide, copper oxide, magnesium oxide and the like. magnesium oxide and silver oxide.
6. Matériau selon l'une quelconque des revendications 1 à 5, comportant en outre 0 à 3% en poids d'un pigment.  The material of any one of claims 1 to 5, further comprising 0 to 3% by weight of a pigment.
7. Matériau selon l'une quelconque des revendications 1 à 6, sous la forme de ruban. 7. Material according to any one of claims 1 to 6, in the form of ribbon.
8. Procédé de fabrication d'un matériau selon l'une quelconque des revendication 1 à 7, comportant les étapes consistant à : The method of manufacturing a material according to any one of claims 1 to 7, comprising the steps of:
mélanger le PTFE, l'oxyde de métal, le lubrifiant, l'agent de mouillabilité et le pigment éventuel, et  mix PTFE, metal oxide, lubricant, wetting agent and any pigment, and
extruder le produit résultant. extrude the resulting product.
9. Câble électrique comportant un ruban selon la revendication 7, enroulé autour d'une âme conductrice. 9. Electrical cable comprising a ribbon according to claim 7, wrapped around a conductive core.
10. Procédé de fabrication du câble électrique selon la revendication 9, par enroulement du ruban autour d'une âme conductrice et cuisson à une température maximum de 450°C.  10. A method of manufacturing the electric cable according to claim 9, by winding the ribbon around a conductive core and baking at a maximum temperature of 450 ° C.
1 1 . Utilisation d'un matériau selon l'une quelconque des revendications 1 à 7, comme isolant électrique.  1 1. Use of a material according to any one of claims 1 to 7 as an electrical insulator.
EP11743273.2A 2010-07-02 2011-06-30 Ptfe material having an anti-corona effect Active EP2589050B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1055386A FR2962128B1 (en) 2010-07-02 2010-07-02 PTFE MATERIAL WITH ANTI-CORONA EFFECT
PCT/FR2011/051529 WO2012001313A2 (en) 2010-07-02 2011-06-30 Ptfe material having an anti-corona effect

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EP2589050A2 true EP2589050A2 (en) 2013-05-08
EP2589050B1 EP2589050B1 (en) 2020-02-26

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EP (1) EP2589050B1 (en)
CN (1) CN103081030B (en)
BR (1) BR112012033721B1 (en)
CA (1) CA2802592A1 (en)
FR (1) FR2962128B1 (en)
RU (1) RU2569368C2 (en)
WO (1) WO2012001313A2 (en)

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RU2569368C2 (en) 2015-11-27
CA2802592A1 (en) 2012-01-05
FR2962128B1 (en) 2013-06-14
BR112012033721B1 (en) 2021-05-18
BR112012033721A2 (en) 2017-11-07
WO2012001313A2 (en) 2012-01-05
US9728299B2 (en) 2017-08-08
FR2962128A1 (en) 2012-01-06
EP2589050B1 (en) 2020-02-26
US20130264090A1 (en) 2013-10-10
CN103081030B (en) 2016-05-11
CN103081030A (en) 2013-05-01
RU2012156264A (en) 2014-08-10
WO2012001313A3 (en) 2012-05-10

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