EP2483894A1 - Medium- or high-voltage electric cable - Google Patents
Medium- or high-voltage electric cableInfo
- Publication number
- EP2483894A1 EP2483894A1 EP10773659A EP10773659A EP2483894A1 EP 2483894 A1 EP2483894 A1 EP 2483894A1 EP 10773659 A EP10773659 A EP 10773659A EP 10773659 A EP10773659 A EP 10773659A EP 2483894 A1 EP2483894 A1 EP 2483894A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- semiconductor
- weight
- electrically insulating
- cable according
- 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
Links
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Classifications
-
- 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
- H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
- H01B7/2813—Protection against damage caused by electrical, chemical or water tree deterioration
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- 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
- H01B3/002—Inhomogeneous material in general
- H01B3/004—Inhomogeneous material in general with conductive additives or conductive layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—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
- H01B3/441—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 alkenes
Definitions
- the present invention relates to an electric cable having improved resistance to wet aging under electrical voltage.
- Medium and high voltage power cables can be in contact with the surrounding humidity during their service life.
- the presence of moisture combined with the presence of an electric field and a polymer material promote the progressive degradation of the insulating properties of the cable.
- EP-1,148,518 discloses a medium voltage power cable having a first semiconductor layer covered by an electrically insulating layer, and a second semiconductor layer covering the electrically insulating layer, thereby forming a three-layer insulation.
- the electrically insulating, extruded and crosslinked layer is obtained from an electrically insulating composition comprising a low density ethylene homopolymer (80 parts by weight) and a polar ethylene copolymer (20 parts by weight) as a compound. delaying the water trees (or WTR compound for Anglicism "Water Tree Retardant").
- This polar ethylene copolymer is of the copolymer type of ethylene and vinyl acetate (EVA), copolymer of ethylene and butyl acrylate (EBA), copolymer of ethylene and ethyl acrylate (EEA), or copolymer ethylene and methyl acrylate (EMA).
- EVA ethylene and vinyl acetate
- EBA copolymer of ethylene and butyl acrylate
- ESA copolymer of ethylene and ethyl acrylate
- EMA copolymer ethylene and methyl acrylate
- the object of the present invention is to overcome the drawbacks of the techniques of the prior art by proposing a new composition intended to be used as a semiconductor layer for electric cable, having resistance to aging, in a humid environment in the presence of an electric field, significantly improved.
- the present invention relates to an electrical cable comprising an electrical conductor, a first semiconductor layer surrounding the electrical conductor, an electrically insulating layer, obtained from an electrically insulating composition, surrounding the first semiconductor layer, and a second semiconductor layer surrounding the electrically insulating layer, characterized in that at least one of the semiconductor layers is obtained from a semiconducting composition comprising an ethylene homopolymer, a nonpolar ethylene copolymer, and a semiconductor charge in an amount sufficient to render the semiconductor composition.
- the first and second semiconductor layers are obtained from said semiconductor composition, the semiconductor charge having the following properties:
- the BET specific surface area according to the ASTM D 6556 standard is strictly less than 500 m 2 / g, and preferably strictly less than 350 m 2 / g, and
- the oil absorption value according to ASTM D 2414-90 is strictly less than 200 ml / 100 g, and preferably lower than at 174 ml / 100 g.
- the mixture of a polar ethylene copolymer with a semiconductor charge is not really suitable for this type of application (ie semiconductor composition) since there has been a progressive and significant degradation of electrically insulating cable properties related to water trees with this type of mixture.
- the advantage of using this type of semiconductor charge is that it has a structure enabling it to facilitate its dispersion in the composition of the invention, and thus to guarantee optimum conductivity properties because of its structure more rigid than that of so-called "high-structure" semiconductor charges having a specific surface area of more than 500 m 2 / g -
- the shrinkage properties of the crosslinked compositions related to the nature of the semiconductor fillers of the invention are advantageously optimized to contribute to a good dimensional stability of the cable.
- semiconductor or “semiconductor” used in the present invention should also be understood to mean “conductor” or “conductor”.
- any copolymer of ethylene does not include polar functions such as acetate groups, acrylates, hydroxyls, nitriles, carboxyls, carbonyls, or any other groups of a polar nature well known in the prior art.
- the homopolymer of ethylene according to the invention can be chosen among a low density polyethylene (LDPE), a linear low density polyethylene (LLDPE), and a very low density polyethylene (VLDPE), or a mixture thereof.
- LDPE low density polyethylene
- LLDPE linear low density polyethylene
- VLDPE very low density polyethylene
- LDPE low density polyethylene
- low density polyethylene can be obtained by a polymerization process in a high pressure tubular reactor, or in an autoclave reactor.
- Low density means a density that can range from 0.910 to
- very low density means a density that can al ler
- the ethylene homopolymer of the invention preferably has a MIF (Melt
- the nonpolar ethylene copolymer according to the invention may comprise a comonomer of the alpha-olefin type, especially of C 3 -C 12 .
- the alpha-olefin comonomer may be selected from propylene, 4-methyl-1-pentene, 1-butene, 1-hexene, 1-octene. It will be preferred to use 1-octene as alpha-olefin to form the ethylene-octene (PEO) copolymer.
- the nonpolar ethylene copolymer may comprise a diene comonomer.
- the diene-type comonomer may be chosen from ethyl iden norbornene, dicyclopentadiene, vinyl norbornene and hexadiene 1-4.
- This type of ethylene copolymer can be in particular an ethylene-propylene terpolymer, such as for example the copolymer of ethylene, propylene and diene (EPDM).
- EPDM ethylene-propylene terpolymer
- the nonpolar ethylene copolymer is obtained from the copolymerization of ethylene with said alpha-olefin, in the presence of a Ziegler-Natta catalyst, a metal oxide catalyst or a catalyst. single site.
- a copolymer obtained by this type of copolymerization is commonly called a metallocene copolymer.
- the "metallocene” nonpolar ethylene copolymers have more regular molecular structures (ie having a “narrow” molecular weight distribution, also called “low polydispersity” polymer) which gives them excellent mechanical properties, especially excellent elongation at break, even in the presence of loads at high rates.
- the metallocene nonpolar ethylene copolymers are more resistant to thermal degradation (ie thermal stress) and aging by cracking (known under the Angl convinced ESCR for "Environmental Stress Cracking Resistance”) than nonpolar ethylene copolymers with substantially identical rate of crystallinity obtained by a different copolymerization process.
- the semiconductor composition comprises at least 50 parts by weight of homopolymer of ethylene per 100 parts of polymer (s) (ie polymer matrix) in said composition, preferably at least 70 parts by weight of ethylene homopolymer per 100 parts of polymer (s) in said composition, and particularly preferably at least 75 parts by weight of ethylene homopolymer per 100 parts of polymer (s) in said composition.
- the semiconductor composition does not comprise more than 85 parts by weight of homopolymer of ethylene per 100 parts of polymer (s) in said composition.
- the semiconductor composition comprises at least 15 parts by weight of non-polar ethylene copolymer per 100 parts by weight of polymer (s) (ie polymer matrix) in said composition, and preferably minus 25 parts by weight of non-polar ethylene copolymer per 100 parts by weight of polymer (s) in said composition.
- the lower limit of 15 parts by weight advantageously preserves the mechanical properties of the semiconductor layer: below 15 parts by weight of non-polar ethylene copolymer, the elongation at break of the semiconductor layer may drop, and thus become insufficient for application in medium and high voltage power cables.
- the semiconductor composition does not comprise more than 30 parts by weight of nonpolar ethylene copolymer per 100 parts by weight of polymer (s) in said composition to facilitate the implementation of the composition.
- the ratio of the weight percentage of ethylene homopolymer to the weight percent of ethylene copolymer in the semiconductor composition is preferably greater than 1 in order to obtain a majority phase of ethylene homopolymer and a minority phase of non-polar ethylene copolymer.
- the polymers that make up the semiconductor composition of the invention are only one or more homopolymers of ethylene and one or more nonpolar ethylene copolymers.
- the semiconductor charge is added to the semiconductor composition to make the latter semi-conductor.
- this composition may comprise from 4 to 40% by weight of semi-conductive filler, preferably at least 15% by weight of semi-solid filler. conductive, and even more preferably at least 25% by weight of semiconductor charge.
- the semiconductor charge may advantageously be chosen from carbon blacks, and graphites, or a mixture thereof.
- an oil absorption value (di (n-butyl) phthalate), according to ASTM D 2414-90 standard, of at least 100 cm 3 / 100g, and a BET specific surface area value, according to ASTM D 6556, of at least 40 m 2 / g -
- carbon blacks having a high degree of purity can be used.
- a high degree of purity can be expressed by a sulfur content of less than 1%, preferably less than 0.5% by weight, and particularly preferably less than 0.25% by weight, in the carbon black considered. this degree of purity being conventionally determined by the measurement method according to ASTM D-1619.
- ash content of less than 2% by weight, preferably less than 1% by weight, and particularly preferably less than 0.5% by weight, in the carbon black under consideration. of ash being conventionally determined by the measurement method according to ASTM D-1506.
- the semiconductor composition according to the invention may further comprise at least one protective agent such as an antioxidant.
- a protective agent such as an antioxidant.
- Antioxidants help to protect the composition of the heat stress generated during cable manufacturing or cable operation.
- the antioxidants are preferably chosen from:
- hindered phenolic antioxidants such as tetrakismethylene (3,5-di-t-butyl-4-hydroxy-hydrocinnamate) methane, octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate / 2,2'-thiodiethylene bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2'-thiobis (6-i "-butyl- 4-methylphenol), 2,2'-methylenebis (6-i "-butyl-4-methylphenol) / 1,2-Bis (3,5-di-t-butyl-4-hydroxyhydrocinnamoyl) hydrazine, [2,2'- oxamido- bis (ethyl 3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate), and 2,2'-oxamido-bis [ethyl 3- (t-
- thioethers such as 4,6-bis (octylthiomethyl) -o-cresol, bis [2-methyl-4- ⁇ 3-n-alkyl (C12 or C14) thiopropionyloxy ⁇ -5-i "butylphenyl] sulfide and Thiobis- [2-t-butyl-5-methyl-4,1-phenylene] bis [3- (dodecylthio) propionate];
- sulfur-based antioxidants such as Dioctadecyl-3,3'-thiodipropionate or Didodecyl-3,3'-thiodipropionate;
- phosphorus-based antioxidants such as phosphites or phosphonates, for instance Tris (2,4-di-t-butylphenyl) phosphite or bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite; and
- amine-type antioxidants such as polymerized 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ), the latter type of antioxidant being particularly preferred in the composition of the invention.
- TMQ polymerized 2,2,4-trimethyl-1,2-dihydroquinoline
- TMQs can have different grades, namely:
- a so-called "standard” grade with a low degree of polymerization that is to say with a residual monomer level greater than 1% by weight and having a residual NaCl content that may range from 100 ppm to more than 800 ppm (parts per million mass);
- the type of stabilizer and its level in the semiconductor composition are conventionally chosen according to the maximum temperature experienced by the polymers during the production of the mixture and during the implementation by extrusion on the cable as well as according to the maximum duration of exposure to this temperature.
- the semiconductor composition can typically comprise of
- antioxidant 0.3% to 2% by weight of antioxidant (s).
- it may comprise at most 0.7% by weight of antioxidant (s), especially when the antioxidant is TMQ.
- Other additives may also be added to the semiconductor composition of the invention such as scorch retarders, crosslinking co-agents, processing agents such as lubricants or waxes, compatibilizers , coupling agents, UV stabilizers and non-conductive fillers.
- the electrically insulating layer of the invention may be obtained from an electrically insulating composition comprising at least 50 parts by weight of homopolymer of ethylene per 100 parts by weight of polymer (s) (ie polymer matrix) in said composition preferably at least 75 parts by weight of homopolymer of ethylene per 100 parts by weight of polymer (s) in said composition.
- the ethylene homopolymer may be selected from low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and very low density polyethylene (VLDPE), or a mixture thereof.
- LDPE low density polyethylene
- LLDPE linear low density polyethylene
- VLDPE very low density polyethylene
- the electrically insulating composition may further comprise a compound limiting the water trees.
- the latter may be a polar ethylene copolymer and, as such, may therefore be part of the polymer matrix.
- the electrically insulating layer of the electric cable is obtained from an electrically insulating composition that does not comprise a compound limiting the water trees.
- the electrically insulating composition comprises a homopolymer of ethylene as the sole polymer in said composition.
- the polymer matrix that composes the electrically insulating composition does not therefore comprise a polar ethylene copolymer which is a compound limiting the water trees.
- the electrically insulating composition comprises 100 parts by weight of ethylene polymer per 100 parts by weight of polymer (s) in the electrically insulating composition.
- this electrically insulating composition does not require additional mixing steps between at least two polymers, as required by the electrically insulating composition of the mixture between the low density ethylene homopolymer and the copolymer.
- the electrically insulating layer of the cable of the invention may further comprise at least one protective agent such as those mentioned for the semiconductor layer (s). In addition, it may comprise other additives such as those mentioned for the semiconductor layer (s).
- At least one of these layers is an extruded layer, preferably two of these three layers are extruded layers, and even more preferentially these three layers are extruded layers.
- At least one of these three layers is a crosslinked layer, preferably two of these three layers are crosslinked layers, and even more preferably these three layers are crosslinked layers.
- the semiconductor composition of the invention as well as the electrically insulating composition, can be crosslinked.
- crosslinking of at least one of these compositions can be carried out by conventional crosslinking techniques well known to those skilled in the art, such as, for example, peroxide crosslinking and / or or hydrosilylation under the action of heat; silane crosslinking in the presence of a crosslinking agent; crosslinking by electron beams, gamma rays, X-rays, or microwaves; photochemically crosslinking such as irradiation under beta radiation, or irradiation under ultraviolet radiation in the presence of a photoinitiator.
- crosslinking techniques well known to those skilled in the art, such as, for example, peroxide crosslinking and / or or hydrosilylation under the action of heat; silane crosslinking in the presence of a crosslinking agent; crosslinking by electron beams, gamma rays, X-rays, or microwaves; photochemically crosslinking such as irradiation under beta radiation, or irradiation under ultraviolet radiation in the presence of a photo
- Peroxide crosslinking under the action of heat is preferred in the context of the invention.
- the composition taken into consideration further comprises a crosslinking agent such as an organic peroxide.
- organic peroxides are well known to those skilled in the art may be used such as for example dicumyl peroxide, f-butylcumylperoxide, 2,5-dimethyl-2,5-di- (i "butylperoxy) hexane di-t-butylperoxide, di- (2-t-butyl-peroxyisopropyl) -benzene.
- the first semiconductor layer, the electrically insulating layer and the second semiconductor layer is a three-layer insulation.
- the electrically insulating layer is in direct physical contact with the first semiconductor layer
- the second semiconductor layer is in direct physical contact with the electrically insulating layer.
- the electrical cable of the invention may further comprise a metal screen surrounding the second semiconductor layer.
- This metal screen may be a "wired” screen, consisting of a set of copper or aluminum conductors arranged around and along the second semiconductor layer, a so-called “ribbon” screen composed of one or more ribbons conductive metal laid helically around the second semiconductor layer, or a so-called “sealed” screen of metal tube type surrounding the second semiconductor layer.
- This last type of screen makes it possible in particular to provide a moisture barrier that tends to penetrate the electrical cable radially.
- All types of metal screens can act as grounding of the electric cable and can carry fault currents, for example in the event of a short circuit in the network concerned.
- the electrical cable of the invention may comprise an outer protective sheath surrounding the second semiconductor layer, or more particularly surrounding said metal screen when it exists.
- This outer protective sheath can be made conventionally from suitable thermoplastic materials such as HDPE, MDPE or LLDPE; or else materials retarding the propagation of the flame or resistant to the propagation of the flame. In particular, if the latter materials do not contain halogen, it is called cladding type HFFR (for the Angl convinced "Halogen Free Flame Retardant").
- the electrical conductor of the cable of the invention may also comprise swelling materials in the presence of moisture to obtain a "sealed core".
- Another object according to the invention relates to a method of manufacturing an electric cable as described above comprising three successive layers. This method comprises the steps of:
- steps i to iii may be performed concomitantly, step iv being carried out after coextrusion and co-deposition of the first semiconductor layer, the electrically insulating layer and the second semiconductor layer. conductive.
- step iv may be performed after each of steps i, ii and iii.
- FIG. 1 showing a schematic view in perspective and in section of an electric cable according to a preferred embodiment according to the invention.
- FIG. 1 showing a schematic view in perspective and in section of an electric cable according to a preferred embodiment according to the invention.
- the medium or high voltage energy cable 1, illustrated in FIG. 1, comprises a central conducting element 2, in particular made of copper or aluminum, and, successively and coaxially, comprises around this element, a first semiconductor layer 3 so-called “internal semiconductor layer”, an electrically insulating layer 4, a second semiconductor layer 5 called “outer semiconductor layer”, a metal screen 6 of the cylindrical tube type, and an outer protective sheath 7, the layers semiconductors 3 and 5 being obtained from a composition according to the invention.
- Layers 3, 4 and 5 are extruded and crosslinked layers by methods well known to those skilled in the art.
- the presence of the metal screen 6 and the outer protective sheath 7 is preferred, but not essential.
- This cable structure is as such of known type and outside the scope of the present invention.
- the “semiconductor layer 1" of Table 1 corresponds to the inner semiconductor layer (eg referenced 3 in FIG. 1) while the “Semiconductor layer 2" of Table 1 corresponds to the outer semiconductor layer ( eg, referenced 5 in Figure 1).
- Cable Ce or Ci Layer Layer Layer semiconductor composition 1 electrically semiconductive 2 insulating insulation
- compositions used to obtain the semiconductor layers referenced in Table 1 are all crosslinkable and comprise an organic peroxide for this purpose. They further include a semiconductor charge and an antioxidant.
- EB1 Semiconductor composition comprising 69.4% by weight of a mixture of 75 parts by weight of Riblene MP20 and 25 parts by weight of Exact 8203, 30% by weight of Vulcan XC-500, and 0.6% by weight TMQ1 weight.
- EB2 Semiconductor composition comprising 69.4% by weight of a mixture of 75 parts by weight of LDPE 1808AN00 and 25 parts by weight of Engage 8450, 30% by weight of Vulcan XC-500, and 0.6% by weight TMQ2 weight.
- EB3 Semiconductor composition comprising 69.4% by weight of a mixture of 75 parts by weight of Riblene MP20 and 25 parts by weight of Exact 8203, 30% by weight of Vulcan XC-500, and 0.6% by weight TMQ2 weight.
- EB4 Semiconductor composition comprising 69.4% by weight of a mixture of 50 parts by weight of Clearflex MPDO and 50 parts by weight of Riblene MP 20, 30% by weight of Vulcan XC-500, and 0.6% by weight of TMQ2.
- EB5 Semiconductor composition comprising 69.4% by weight of a mixture of 75 parts by weight of Riblene MP20 and 25 parts by weight of Exact 8203, 30% by weight of Conductex 7055 Ultra, and 0.6% by weight of TMQ1.
- EB6 Semiconductor composition comprising 69.4% by weight of a mixture of 75 parts by weight of Novex 19N430 and 25 parts by weight of Exact 8203, 30% by weight of Vulcan XC-500, and 0.6% by weight of TMQ3.
- EB7 Semiconductor composition comprising 69.4% by weight of a mixture of 75 parts by weight of LDPE 2008TN00 and 25 parts by weight of Exact 8203, 30% by weight of Vulcan XC-500, and 0.6% by weight of TMQ1.
- Semiconductor composition comprising 61.4% by weight of a mixture of 70 parts by weight of LDPE 2015T and 30 parts by weight of Exact 8203, 38% by weight of Purex HS 45, and 0.6% by weight of TMQ1 .
- Clearflex MPDO is a commercial reference of Polimeri Europa SpA a copolymer of ethylene and apolar alpha-olefin called VLDPE (Very Low Density Polyethylene) whose density is 0.900 g / cm 3 and the MFI is 7.5 g / 10min;
- Range MP20 is a commercial reference of the Polimeri Europa SpA company of a homopolymer of low density ethylene obtained by polymerization process in a high pressure autoclave reactor, the density of which is 0.919 g / cm 3 and the MFI is 7.5 g / 10min;
- LDPE 1808AN00 is a commercial reference of SABIC Europe BV of a homopolymer of low density ethylene obtained by polymerization process in a high pressure autoclave reactor, whose density is 0.920 g / cm 3 and the MFI is 7.5 g / 10 min;
- Novex 19N430 is a commercial reference of the company INEOS O & P Europe of a homopolymer of low density ethylene obtained by polymerization process in a high pressure autoclave reactor, whose density is 0.920 g / cm 3 , and the MFI is 7.5 g / 10min;
- LDPE 2008TN00 is a commercial reference of SABIC Europe BV of a homopolymer of low density ethylene obtained by polymerization process in a high pressure tubular reactor, whose density is 0.921 g / cm 3 and the MFI is 7.5 g / 10 min;
- LDPE 2015 T is a commercial reference of SABIC Europe BV of a homopolymer of low density ethylene obtained by polymerization process in a high pressure tubular reactor, the density of which is 0.920 g / cm 3 and the FI is 15 g / 10 min;
- “Engage 8450” is a commercial reference of The Dow Chemical Company of a copolymer of ethylene and apolar octene from a polymerization process with a metallocene catalyst, the density of this copolymer being 0.902 g / cm. 3 ;
- Exact 8203 is a commercial reference of the company DEX Plastomers of a copolymer of ethylene and apolar octene from a polymerization process with a metallocene catalyst, the density of this copolymer being 0.882 g / cm 3 ;
- Vulcan XC-500 is a commercial reference of Cabot Coporation of a conductive carbon black having BET specific surface area according to ASTM D 6556 standard of 58 m 2 / g oil absorption according to ASTM D 2414- 90 of 150 ml / 100 g, a sulfur content of less than 0.1% by weight and an ash content of less than 0.1% by weight;
- Conductex 7055 Ultra is a commercial reference of Columbian Chemicals Company of a conductive carbon black having a BET surface area according to ASTM D 6556 of 55 m 2 / g, an oil absorption according to ASTM D 2414-90 of 170 ml / 100g, a sulfur content of less than 0.5% by weight and an ash content of less than 0.075% by weight;
- Purex HS 45 is a commercial reference of the Evonik Carbon Black company of an "improved N550" type carbon black having a BET specific surface area according to the ASTM D 6556 standard of 41 m 2 / g, an oil absorption according to ASTM D 2414-90 standard of 121 ml / 100g, a sulfur content less than 0.5% by weight and an ash content of less than 0.35% by weight;
- TMQ1 is an antioxidant of the 2,2,4-trimethyl-1,2-dihydroquinoline type known as "low residual salt", marketed by Lanxess Germany GmbH under the reference Vulkanox HS / LG “low knows”;
- TMQ2 is an antioxidant of the type 2,2,4-trimethyl-1,2 dihydroquinoline said "standard", sold by Lanxess GmbH under the reference Vulkanox HS / LG;
- TMQ3 is an antioxidant type 2,2,4-trimethyl-1,2 dihydroquinoline said "high degree of polymerization” marketed by the company Songwon Industrial Co. Ltd. under the reference Antioxidant FR SB.
- compositions used to obtain the electrically insulating layers referenced in Table 1. These compositions are all crosslinkable and comprise an organic peroxide for this purpose. They further include an antioxidant.
- compositions RI, and EB1 to EB8 referenced in Table 2, for each layer to be considered are metered and mixed respectively in a continuous mixer of the BUSS co-kneader type, twin-screw extruder or another type mixer suitable for charged thermoplastic mixtures.
- the mixture is then extruded in the form of rods, then cooled and dried to form granules.
- These granules are then impregnated with a liquid organic peroxide whose rate is adjusted according to the amount of polymer matrix to be crosslinked.
- compositions LE, HF_sc, LH and HF_ei3 referenced in Tables 2 and 3 are ready-to-use compositions.
- these compositions are directly introduced into a single-screw extruder in order to extrude and deposit each of said compositions around the copper electrical conductor, according to the type of layers and their positioning mentioned in FIG. table 1.
- the various compositions are extruded one after the other to successively surround the copper electrical conductor, and thus form the various three-layer isolations as mentioned in Table 1.
- each trilayer insulation is crosslinked under the action of heat at a temperature above the decomposition temperature of the organic peroxide included in each of the three layers.
- the electrical cables Cc1 to Cc3 and C11 to C19 are thus obtained respectively, each comprising three extruded and crosslinked layers. Aging test and breakdown voltage
- the breakdown voltage (in kV / mm) of the electrical cable corresponds to the voltage necessary to form an electric arc within the cable. It is typically reduced to the maximum electric field at the interface between the first semiconductor layer (or inner semiconductor layer) and the electrically insulating layer of the electrical cable.
- the trilayers of these two cables both comprise an electrically insulating layer of the same nature as the three-layers of the cables C11-C16 and C18 and C19, while their semiconductor layers are respectively composed of a non-polar matrix (for the Cc2 cable) and a polar matrix (for the Cc3 cable).
- the combination of semiconductor layers according to the invention with an electrically insulating layer free of limiting compound water trees has a very good resistance to aging and resistance to water trees improved, while remaining very economical .
- the trilayer of the cable Ci7 exhibits water tree resistance properties after 1000h (81 kV / mm) significantly higher than those of the cables Ccl (55 kV / mm), Cc2 (41 kV / mm). ) and Cc3 (40 kV / mm), and more particularly to those of the cable Ccl which comprises, as the tricouche of the cable Ci7, an electrically insulating layer based on a homopolymer of ethylene combined with a polar ethylene copolymer. This difference in results is due to the nature of the semiconductor layer of the trilayer.
- the preparation of the electrically insulating layer of the tricouche of the cable Ci7 includes various mixing steps (between the polymers that make up this layer), the combination of this layer with a semiconductor layer according to the invention induces a synergistic effect of more significant since the breakdown voltage is the highest of Table 4, and reaches 80 KV / mm after an aging of 1000h.
- the retraction test measures the ability of a plastic to retain a shape given to it by different forming techniques such as extrusion, molding and the like.
- shrink tests must be carried out, because it must be ensured that the materials constituting the cable retain a good dimensional stability during the life of the cable. Without this dimensional stability, especially to be considered in the longitudinal direction of the cable, that is to say in the direction of the conductive core over the entire length of the cable, defects may occur in particular at the connection points (joints and terminations ) and cause a failure of the power cable.
- These tests are carried out on cable samples, for example according to IEC 60502-2 and IEC 60811-1-3 standards, for the electrically insulating layers of crosslinked polyethylene of medium voltage power cables for rated voltages from 1 to 30 kV.
- shrink tests are commonly performed on the outer sheaths of cable protection.
- a quantity of material of the curable semiconducting composition ensuring the proper filling of the entire cavity, is introduced into the cavity of the unheated mold and previously coated with a thin polyester film (thickness 50 ⁇ m) which allows demolding. easy.
- the amount of material to use varies between 80 and 100 g depending on the density of the composition.
- the mold is closed and placed in an automated laboratory press preheated to 120 ° C. The temperature of the assembly is expected to stabilize at 120 ° C.
- An automatic molding cycle is then started comprising the following steps:
- crosslinking of the material at 190 ° C. for 20 minutes under a pressure of 200 bar
- the molded plates are demolded and separated from the polyester films. Then, the plates are degassed for 5 days at room temperature. During degassing, the plates are maintained under a slight pressure to prevent any deformation of the plates during these 5 days.
- the molded plates are laid flat in a hot air oven preheated to 130 ° C and held under a slight pressure to prevent deformation. The heat treatment at this temperature is maintained for 60 minutes after temperature stabilization. Then, the molded plates are taken from the oven to cool to room temperature for 24 hours while keeping light pressure on the plates to prevent deformation. The molded plates are then transferred to a measuring room maintained at 20 ° C where they are stored for at least 3 hours. The dimensions "width" and "depth” are measured using a digital caliper. Retraction is calculated by comparing the dimensions (width and depth) of the mold cavity with the width and depth measured from each molded plate. Retraction is expressed as a percentage.
- Table 5 summarizes the results obtained from the shrinkage test for the semiconductor compositions EB6 and EB8, as well as two other semiconductor compositions R2 and R3 comprising a carbon black having properties that are not in conformity with those claimed in the present invention.
- the details of the compositions R2 and R3 are mentioned in Table 6 below.
- LDPE 2101TN00 is a commercial reference of SABIC Europe BV of a low density ethylene homopolymer obtained by polymerization process in a high pressure tubular reactor, the density of which is 0.920 g / cm 3 and the MFI is 0.85 g / 10 min;
- Ketjenblack EC300-J is a commercial reference of the company AkzoNobel Functional Chemicals BV a so-called "extra-conductive" carbon black having a BET specific surface area according to the ASTM D 6556 standard of 800 m 2 / g, an absorption of oil according to ASTM D 2414-90 of
- Irganox 1081 is a commercial reference of a thiophenolic antioxidant of the type 2,2'-Thiobis (6-t-butyl-4-methylphenol) marketed by Ciba Specialty Chemicals Inc.
- compositions R2 and R3 referenced in Table 6 are dosed and mixed respectively in a continuous mixer of the BUSS co-kneader type, twin-screw extruder or another type of mixer suitable for charged thermoplastic mixtures.
- the mixture is then extruded in the form of rods, then cooled and dried to form granules.
- These granules are then impregnated with a liquid organic peroxide whose rate is adjusted according to the amount of polymer matrix to be crosslinked.
- Table 5 it is observed that after the heat treatment, the compositions of the invention EB6 and EB8 show the lowest shrinkage rates, while the compositions R2 and R3 show particularly high shrinkage rates.
- These two compositions use a carbon black of which:
- the BET specific surface area according to ASTM D 3037 is greater than 500 m 2 / g
- the oil absorption value according to ASTM D 2414-90 is greater than 200 ml / 100 g.
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Abstract
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Application Number | Priority Date | Filing Date | Title |
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FR0956773A FR2950728B1 (en) | 2009-09-30 | 2009-09-30 | ELECTRICAL CABLE WITH MEDIUM OR HIGH VOLTAGE |
PCT/FR2010/052050 WO2011039474A1 (en) | 2009-09-30 | 2010-09-29 | Medium- or high-voltage electric cable |
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EP (1) | EP2483894B1 (en) |
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FR3006493A1 (en) * | 2013-06-04 | 2014-12-05 | Nexans | ELECTRICAL CABLE WITH MEDIUM OR HIGH VOLTAGE |
FR3021451B1 (en) * | 2014-05-20 | 2017-12-15 | Nexans | ELECTRICAL CABLE COMPRISING A RETICULATED LAYER |
CN105405510A (en) * | 2015-12-07 | 2016-03-16 | 无锡裕德电缆科技有限公司 | Direct current traction anti-corrosion power cable for rail transit of 1,500V or less |
DE102015016088A1 (en) * | 2015-12-11 | 2017-06-14 | Schmidt Hochstromtechnik GmbH | high power coaxial |
CN109689772B (en) | 2016-09-09 | 2021-07-30 | 莱尼电缆有限公司 | Polymer composition with high flexibility and flame retardancy |
US11248111B2 (en) | 2016-09-09 | 2022-02-15 | Leoni Kabel Gmbh | Conjunction device such as a cable and polymer composition for preparing same |
CN109689768B (en) | 2016-09-09 | 2021-07-30 | 莱尼电缆有限公司 | Strip-shaped element and polymer composition for producing same |
JP6795481B2 (en) | 2017-11-07 | 2020-12-02 | 日立金属株式会社 | Insulated wire |
JP6756693B2 (en) * | 2017-11-07 | 2020-09-16 | 日立金属株式会社 | Insulated wire |
JP6756692B2 (en) * | 2017-11-07 | 2020-09-16 | 日立金属株式会社 | Insulated wire |
FR3079067B1 (en) * | 2018-03-19 | 2020-03-20 | Nexans | ELECTRIC CABLE COMPRISING AN EASILY PEELABLE POLYMERIC LAYER |
BR112020019372A2 (en) * | 2018-03-28 | 2020-12-29 | Dow Global Technologies Llc | NON-POLAR AND BLACK ORGANIC POLYMER COMPOSITE OF ULTRA-DOWN WET SMOKE |
FR3090985B1 (en) * | 2018-12-21 | 2020-12-18 | Nexans | Cable comprising an easily peelable semiconductor layer |
FR3090988B1 (en) * | 2018-12-21 | 2020-12-18 | Nexans | Electric cable resistant to water trees |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60235304A (en) * | 1984-05-08 | 1985-11-22 | 株式会社フジクラ | Dc power cable |
US5246783A (en) * | 1991-08-15 | 1993-09-21 | Exxon Chemical Patents Inc. | Electrical devices comprising polymeric insulating or semiconducting members |
JP3047377B2 (en) * | 1992-07-24 | 2000-05-29 | 矢崎総業株式会社 | Low water absorption semiconductive layer for power cable |
JPH08298032A (en) * | 1995-04-25 | 1996-11-12 | Nippon Unicar Co Ltd | Manufacture of crosslinked polyethylene insulated power cable |
JPH0952985A (en) * | 1995-08-10 | 1997-02-25 | Yazaki Corp | Composition for semiconducting layer of power cable |
ATE255270T1 (en) | 2000-04-17 | 2003-12-15 | Nexans | METHOD FOR PRODUCING CROSS-LINKED POLYETHYLENE COVERED CONDUIT WIRES |
-
2009
- 2009-09-30 FR FR0956773A patent/FR2950728B1/en not_active Expired - Fee Related
-
2010
- 2010-09-29 US US13/496,557 patent/US20120227997A1/en not_active Abandoned
- 2010-09-29 EP EP10773659.7A patent/EP2483894B1/en active Active
- 2010-09-29 ES ES10773659.7T patent/ES2455545T3/en active Active
- 2010-09-29 WO PCT/FR2010/052050 patent/WO2011039474A1/en active Application Filing
Non-Patent Citations (1)
Title |
---|
See references of WO2011039474A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO2011039474A1 (en) | 2011-04-07 |
FR2950728B1 (en) | 2012-08-17 |
ES2455545T3 (en) | 2014-04-16 |
US20120227997A1 (en) | 2012-09-13 |
EP2483894B1 (en) | 2014-01-15 |
FR2950728A1 (en) | 2011-04-01 |
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